WO2006104053A1 - 紙容器 - Google Patents
紙容器 Download PDFInfo
- Publication number
- WO2006104053A1 WO2006104053A1 PCT/JP2006/306002 JP2006306002W WO2006104053A1 WO 2006104053 A1 WO2006104053 A1 WO 2006104053A1 JP 2006306002 W JP2006306002 W JP 2006306002W WO 2006104053 A1 WO2006104053 A1 WO 2006104053A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- laminate
- gas
- group
- gas barrier
- Prior art date
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Classifications
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Definitions
- the present invention relates to a paper container having a gas-nozzle property having a window through which contents can be confirmed.
- the present invention also relates to a paper container having a heat resistance that can withstand a retort sterilization process and having excellent gas noriability in a container including a paper layer.
- Such a paper container of the present invention is also suitable for microwave heating.
- Patent Documents 1 to 3 describe a paper container in which a paper layer is provided with a notch and the notch is covered with a transparent material.
- Patent Document 1 there is no description about the gas barrier material.
- Patent Documents 2 and 3 have a description of covering a notch with a gas barrier material.
- the gas noble material Patent Document 2 discloses a metal oxide-deposited biaxially stretched plastic film force.
- Patent Document 3 discloses a gas barrier material such as a film of polybulal alcohol, ethylene acetate butyl copolymer oxide, or polyethylene terephthalate. Polyamide, polybulal alcohol, ethylene acetate copolymer copolymer, etc. coated with polysalt-vinylidene, or deposited with inorganic materials such as acid and aluminum oxide Examples include films.
- a laminate used for a paper container a laminate in which low-density polyethylene having thermal adhesiveness, water resistance and the like is laminated on the inner surface or both sides of the paper as a base material is used. in use.
- low-density polyethylene such as linear low-density polyethylene resin, heat-adhesive linear low-density polyethylene resin, high-density polyethylene resin, and polypropylene resin
- a heat resistant polyolefin is selected.
- Patent Document 4 describes a laminated material including a metallized stretched polyester (used), a metallized stretched polypropylene (usually using aluminum), ethylene z-butyl alcohol, and polybulual alcohol.
- the present situation is that there is no paper container that has a sufficient gas-nore property in various shapes that can be retorted and that has good moldability.
- Patent Document 5 describes a vacuum heat insulator using a gas noble layer in which aluminum is vapor-deposited on a film made of an ethylene-butyl alcohol copolymer resin.
- Patent Document 6 in order to cope with such a problem, a resin and an inorganic layered composite are further formed on a metal compound deposition layer such as alumina deposited on a substrate resin.
- a vacuum heat insulator using a gas barrier material having a gas barrier layer composed of the above has been proposed, the gas barrier property is still insufficient, and the heat insulating effect is not sufficiently maintained over a long period of time.
- plastic infusion containers include those with a nog shape and those with a bottle shape.
- the infusion bag in the form of a nog is made of a polyolefin resin such as polyethylene, such as a polysalt resin resin.
- a polyolefin resin such as polyethylene, such as a polysalt resin resin.
- Polyolefin-based fats are not sufficient in gastrinogenicity, and there is a problem that infusions such as amino acid preparations, glucose preparations, fat emulsions, electrolyte infusions, etc. are easily altered by gases such as oxygen.
- Polysalt vinyl vinyl vinyl resin is Because it contains additives such as plasticizers and stabilizers, its elution is a concern.
- polyolefin polyolefin resin has a problem that it is inferior in gasnolia property.
- the outside of the infusion bag made of polyolefin or the like is provided with a separately prepared bag having gas barrier properties, that is, an ethylene vinyl alcohol copolymer resin, polysalt ⁇ Double-wrapped with exterior materials such as multilayer films composed of biurydene, for example, a multilayer film composed of a polyester layer, an ethylene butyl alcohol copolymer layer, and an unstretched polypropylene layer. (See 7).
- Patent Document 8 describes an infusion bag using polyamide resin.
- polyamide resin does not have sufficient noria properties for applications that require a high degree of gas noria properties, and tends to lower barrier properties when subjected to high-temperature steam sterilization.
- Patent Document 9 describes a force in which an infusion bag in which a gas nore coating layer is formed on the outer surface of an infusion bag and is covered with a protective agent is described.
- Noria layers described here are vapor-deposited alumina, silica, etc. Due to the lack of flexibility, there is a concern that the barrier property will be reduced due to damage during transportation and handling of the bag. EVOH, PVA, and PVDC will also have a lower barrier property when subjected to high-temperature steam sterilization. In addition, since PVDC contains chlorine, it is necessary to pay attention to disposal and incineration.
- a cover material a film made of a polysalt-vinylidene-based resin (hereinafter referred to as a PVDC film), a film made of an ethylene butyl alcohol copolymer (hereinafter referred to as an EVOH film), a silica film on a base film. , Alumina, aluminum, etc.
- a cover material including a PVDC film
- Patent Document 11 describes a cover material including an EVOH film
- Patent Document 12 describes a cover material including a vapor deposition film.
- the oxygen noria property may satisfy a desired performance.
- incineration causes the generation of toxic gases such as dioxin, which impairs environmental suitability.
- an EVOH film when used, it exhibits excellent oxygen barrier properties in a low humidity and atmosphere, but has a problem that the oxygen barrier properties are reduced when the EVOH film absorbs moisture.
- the inorganic vapor deposition layer which is a gas barrier layer
- the gas barrier property is easily lowered. For example, if a crack occurs in the printing process or lamination process for manufacturing a multilayer laminate from a vapor-deposited film and another film, or if many containers with lids are transported, the containers with lids are stacked and transported. If the gas barrier layer is cracked by vibration during transportation, the gas barrier property may be lowered.
- Laminate tube containers used for packaging cosmetics, medicines, pharmaceuticals, toiletries such as toothpaste, foods such as kneading, wasabi, etc. must be excellent in gas nolia and aroma retention.
- a laminated material using a resin film having no aluminum foil and having a vapor deposition layer of aluminum has been used in many cases.
- the packaging material design was limited because the laminated material could not be transparent.
- it was difficult to see through the contents it was not easy to check the contents of the contents and the remaining amount, and it was inconvenient to squeeze the contents to the end.
- the tube container is used as a packaging device and then disposed of as garbage, aluminum remains, resulting in poor disposal and residual aluminum damaging the incinerator.
- a vacuum deposition method is used.
- a transparent vapor-deposited film having a vapor-deposited layer of inorganic oxide, a film using a polysalt-vinylidene-based resin, and a film using an ethylene butyl alcohol copolymer can be listed. These are also used as laminated tube containers (see, for example, Patent Documents 13 and 14).
- the transparent vapor-deposited film causes defects such as cracks in the vapor-deposited layer, which is the gas barrier layer, in the printing process and the lamination process until the laminated tube container is manufactured.
- defects such as cracks in the vapor-deposited layer, which is the gas barrier layer, in the printing process and the lamination process until the laminated tube container is manufactured.
- the ethylene-vinyl alcohol copolymer is a barrier film having excellent gas barrier properties, transparency, and environmental! It has a problem that the performance is lowered.
- Vacuum packaging characterized by vacuum degassing inside the bag after being sealed in the bag is widely used.
- heat sterilization is performed after vacuum packaging, but there are cases where the contents are vacuum-packed in a sterile state and not heat sterilized.
- the oxygen concentration inside the packaging material must be low.
- a material that can easily follow the shape according to the unevenness of the food and has high gas nature is used.
- Such a gas packaging material having a high gas-nore property includes a polychlorinated vinylidene-based resin layer, an ethylene acetate butyl copolymer acid oxide (EVOH) layer, an alcohol Laminates having vapor deposition layers such as minimum foil layers, silicon oxide, and aluminum oxide have been used.
- EVOH ethylene acetate butyl copolymer acid oxide
- Laminates having vapor deposition layers such as minimum foil layers, silicon oxide, and aluminum oxide have been used.
- Laminate including aluminum foil layer, polysalt / vinylidene In recent years, the use of laminates containing a resin layer tends to be refrained from environmental considerations.
- Laminates containing aluminum foil remain as a residue when incinerated after use, and laminates containing polysalt-vinylidene-based resin layers contain harmful compounds containing chlorine during incineration after use. Each has the problem that it may be generated. Furthermore, it has been pointed out that the laminated body including the aluminum foil layer is opaque, so that the state of the contents cannot be confirmed, and a metal detector cannot be used for the contents inspection.
- a laminate having a gas barrier layer formed by depositing an inorganic oxide such as aluminum oxide or silicon oxide on a base film is transparent and has excellent gas barrier properties. Due to deformation of the packaging material during vacuum packaging, In addition, cracks and pinholes are generated in the deposited layer, and the gas noria property is lowered. In other words, the packaging material is deformed according to the unevenness of the contents, or cracks or pinhole defects occur in the deposited layer by bending at the boundary between the part in contact with the contents and the heat seal part. In addition, there is a problem that gas noria properties deteriorate due to expansion and contraction during heat sterilization treatment, impact and bending when the package is handled, and cracks and pinholes are generated in the deposited layer. .
- Laminates with an ethylene vinyl acetate copolymer oxide (EVOH) layer as a gas nolia layer have excellent gas barrier properties, but the gas barrier properties deteriorate due to the heat sterilization treatment that follows the vacuum packaging described above.
- the storage period of the food which is the content
- the packaging bag is deformed according to the unevenness of the food, In addition, the boundary between the part in contact with the food and the heat seal part is bent, so that the gas noliaability is lowered, and as a result, the storage period of the food is shortened.
- liquid containers such as liquid detergents, shampoos and rinses, liquid drinks such as soft drinks, and liquids and fluids of foods are rigid containers such as glass bottles, metal cans, and plastic bottles. Had been filled. However, in such a container, the packaging cost is high, and the packaging material cannot be reduced at the time of disposal. Therefore, plastic film fates with a spout on one of the sealing surfaces have become widespread as a lightweight, inexpensive, and simple container used for packaging recently.
- spouted bouch containers standing (Fig. 1) and pillow type (Fig. 2).
- the plastic film and the layer structure used for the spouted bouch may be selected according to the properties of the contents to be filled in the bouch. For example, a low-cost packaging such as a detergent refill packaging bag is required. A laminated film with a layer structure may be used, but when filling contents that require preservation, such as beverages, seasonings, and retort foods, aluminum foil or an inorganic vapor deposition layer is applied. It is preferable to use a laminated film of three or more layers including a noria layer such as a film, a gas-nozzle resin film, or a film coated with them.
- a noria layer such as a film, a gas-nozzle resin film, or a film coated with them.
- a packaging bag using polyamide resin has been proposed as a method for imparting gas noliacity to a bouch including a spouted bouch (see, for example, Patent Document 8).
- polyamide resin does not have sufficient noreia for applications that require a high degree of gasnolianess, and the barrier property tends to decrease when retort sterilization is performed.
- vinyl chloride and polyacrylonitrile have the potential to become a source of harmful substances during disposal and incineration.
- metal foil is excellent in gas-nore properties, but the contents cannot be confirmed through the packaging material, a metal detector cannot be used for inspection, and the metal layer is separated from other layers when discarded after use.
- the inorganic oxide deposition layer is a thin film with a maximum of 800 A or less and is transparent. It is handled in the same way as printing ink and does not cause environmental problems that do not require separate incineration.
- the packaging bag with film stack strength is not flexible enough to prevent bending during filling and distribution, and pulling due to changes in internal pressure during sterilization cooking.
- the attachment part is damaged particularly in the edge part of the heat seal part of the spout pouch main body, leading to deterioration of the gas noria property as a container.
- Patent Document 1 Japanese Patent Laid-Open No. 10-194273
- Patent Document 2 Japanese Patent Laid-Open No. 2003-054537
- Patent Document 3 Japanese Patent Laid-Open No. 11-227752
- Patent Document 4 Japanese Patent Publication No. 11-508502
- Patent Document 5 JP-A-10-122477
- Patent Document 6 Japanese Patent Laid-Open No. 11-257574
- Patent Document 7 Japanese Patent Application Laid-Open No. 09-262943
- Patent Document 8 JP 2001-328681 A
- Patent Document 9 Japanese Unexamined Patent Application Publication No. 2005-040489
- Patent Document 10 Japanese Patent Publication No.57-030745
- Patent Document 11 Japanese Patent Laid-Open No. 09-239911
- Patent Document 12 Japanese Unexamined Patent Application Publication No. 2005-8160
- Patent Document 13 Japanese Patent Laid-Open No. 11-129380
- Patent Document 14 Japanese Patent Application Laid-Open No. 07-308994
- An object of the present invention is to provide a paper container with a window that is easy to produce and has no gas noria properties when the container is transported, and has excellent gas noria properties.
- Another object of the present invention is to provide a retort paper container that can be retorted, has excellent molding processability, and has excellent gas barrier properties.
- the inventors of the present invention have a paper container having at least a paper layer and also having a laminate strength.
- the paper layer is provided with a notch, and the notch is provided with a gas barrier property.
- the laminate is covered, and the gas nore laminate is a gas nore laminate including a base material and a gas nore layer laminated on at least one surface of the base material, for example, FIG. 1 and FIG. 2.
- the gas nolia layer is composed of a yarn and a composition containing a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride base
- the inventors have found that the above object can be achieved when at least a part of the COO group contained in at least one functional group is neutralized with a metal ion having a valence of 2 or more, and the present invention has been completed.
- the present invention relates to a paper container having at least a paper layer, wherein the paper layer has a notch, and the gas barrier laminate covers the notch, and the gas barrier laminate is provided.
- the body includes a base material and a gas noria layer laminated on at least one surface of the base material, and the gas noria layer has at least one selected from a carboxyl group and a carboxylic acid anhydride base
- a composition comprising a polymer containing a functional group, wherein at least part of the COO group contained in the at least one functional group is neutralized with a metal ion having a valence of 2 or more. It is a paper container.
- the present inventors have found that, in a paper container having at least a paper layer, a heat-resistant polyolefin layer, and a gas nolia layer, a carboxyl group and a carboxylic acid are used as the gas barrier layer.
- An anhydride base force is a composition force including a polymer containing at least one functional group selected, and at least a part of the COO group contained in the at least one functional group is neutralized with a metal ion having two or more valences,
- the present inventors have found that a retort treatment can be performed by adopting a gas barrier layer, a retort paper container having excellent gas barrier properties and excellent molding processability, and the present invention has been completed.
- another embodiment of the present invention provides a paper container having at least a paper layer, a heat-resistant polyolefin layer, and a gas nolia layer, wherein the gas barrier layer is selected from a carboxyl group and a carboxylic acid anhydride base.
- Composition comprising a polymer containing one functional group
- the retort paper container is characterized in that at least a part of the COO group contained in the at least one functional group is neutralized with a metal ion having a valence of 2 or more.
- a paper container having at least a paper layer and also having a laminate strength is provided with a notch in the paper layer, and the gas barrier laminate covers the notch.
- the present invention is characterized in that the gas noria layer contained in the gas noria laminate is a specific gas noria layer.
- this specific gas barrier layer may hereinafter be referred to as “the gas barrier layer of the present invention”.
- a laminate in which this specific gas nolia layer, which will be described in detail later, is laminated on at least one surface of the substrate may be referred to as “the gas noria laminate of the present invention”.
- the type of paper container is not particularly limited, but for example, single 'board type gobel' top type, brick (brick) type, rectangular parallelepiped type, conical type paper container, cup type paper container, spiral type paper Examples include containers and insert-molded paper containers.
- polyolefin As a laminate having at least a paper layer used in the paper container of the present invention, polyolefin is used.
- the paper layer that constitutes the laminate including the paper layer is a layer that maintains shape retention when formed into a container.
- special characteristics such as water resistance and oil resistance are required when used as beverage containers.
- white paperboard, marl ball, milk carton base paper, cup base paper, ivory paper, etc. can be used.
- the polyolefin (PO) layer includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene acetate butyl copolymer, ethylene ⁇ -olefin composite weight.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a resin having a polypropylene strength, or a sheet formed from these.
- linear (linear) low density polyethylene and polypropylene are preferred.
- any of the cocoon layers constituting the laminate is also composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- the eaves layer arranged in the outermost layer and the innermost layer of the laminate is not stretched. It is preferably composed of stretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- any PO layer is linear low density polyethylene or polypropylene from the viewpoint of heat resistance.
- unstretched polypropylene which is preferably composed of unstretched linear low-density polyethylene and unstretched polypropylene.
- a method for forming a polyolefin (PO) layer an unstretched polyolefin film or a stretched polyolefin film facilitated in advance, a film constituting other layers and a known dry lamination method, wet A method of laminating by a lamination method, a hot melt lamination method or the like, or a method of forming a polyolefin layer on a film constituting another layer by a well-known T-die extrusion method or the like can be employed.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive resin, or the like.
- the thickness of the polypropylene layer is preferably in the range of 10 to 200 ⁇ m, more preferably in the range of 20 to 150 m from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like. ! /
- a laminate including the gas barrier layer that is, a laminate including a gas layer used in a portion other than the notch portion of the paper layer, a layer made of an aluminum foil cover, a vapor deposition layer made of silicon oxide.
- a laminated body comprising a gas barrier layer having a vapor-deposited layer made of silicon oxide, a vapor-deposited layer made of aluminum oxide, a layer made of polybutyl alcohol, etc.
- a gas noorier laminate on at least one side of the substrate, and the present invention Examples of such a gas noorier laminate may be mentioned.
- An adhesive layer can be appropriately provided between the base material and the gas nozzle layer.
- the base material a base material similar to the base material used in the gas noble laminate of the present invention can be used.
- the laminated body including the gas noble layer is preferably the gas noble laminated body of the present invention.
- the gas burrs covering the notch portions described later which are preferable in terms of surface strength such as gas nooriety, workability, and impact resistance. More preferably, the same gas noble layer as that of the porous laminate is included.
- Configure the paper container When the gas-noria laminate that covers the cutout portions of the noria layer and the paper layer is the same, the container with a window can be easily manufactured.
- a laminate of a polyethylene (PE) layer, a Z paper layer, and a ZPE layer is prepared in advance by an extrusion lamination method, and then a notch is provided at a predetermined location.
- the laminate comprising the gasnolia laminate ZPE layer of the present invention can be produced, and by laminating both, a laminate for a paper container with a window can be produced. .
- the laminate including the gas-nolia laminate covering the cutout portion of the paper layer is a part of the laminate constituting the paper container, that is, among the layers constituting the laminate, the paper layer or the paper layer and other layers. It may be provided so that the contents can be confirmed by cutting out the layer including the layer, or it may be provided so as to be attached to the outside of the container or Z and the inner cover of the container so as to cover the notch of the paper layer. Good.
- the laminate including the gas barrier laminate is preferably provided as a part of the laminate constituting the paper container.
- a laminate including a gas-nolia laminate that is attached from the outside of the container and Z or from the inside of the container so as to cover the notch of the paper layer will be described.
- the gas barrier laminate is preferably attached via an adhesive layer which is also a polyolefin linker provided on one side or both sides thereof.
- the adhesive layer that also has polyolefin power provided on one or both sides of the gas nori laminate, it is firmly heat-bonded to the outer layer of the paper container and the polyolefin layer provided on the Z or inner layer so that the contents do not leak. It is preferable that the adhesive layer is compatible with the polyolefin layer provided in the inner layer of the paper container.
- the adhesive layer may be appropriately selected and used depending on the type of polyolefin layer provided on the outer layer and the Z or inner layer of the paper container.
- the laminate including the gas barrier laminate covering the cutout portion of the paper layer include a polyolefin layer Z, a gasnolia laminate Z, a polyolefin layer, and a gas nolia laminate Z-olefin layer.
- An adhesive layer can be appropriately provided between the olefin layer and the gas nori laminate.
- the olefin layer include those similar to the olefin layer exemplified in the laminate having a paper layer.
- Preferred polyolefins applicable to the polyolefin layer are unstretched low density polyolefin, unstretched linear low density polyolefin, unstretched Polypropylene.
- the adhesive layer composed of the polyolefin layer heat-adhesive resin layer on one side or both sides of the gas- noble laminate of the present invention the well-known T-die extrusion method, dry lamination method, etc. It can form by using suitably. Moreover, an anchor coat agent etc. can also be used as needed. Further, the sealing sheet may be produced using a known co-extrusion method or the like. The thickness of the sealing sheet is preferably about 20 to 150 ⁇ m from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like.
- a protective sheet may be provided so as to further cover the laminate.
- the protective sheet is composed of a heat-adhesive resin layer and serves to protect the laminate from the contents so that the laminate including the gas barrier laminate covering the notch does not come into contact with the contents. is there.
- any heat-bonding resin layer provided on the inner layer of the paper container and the contents may be heat-bonded to such an extent that the contents do not penetrate into the laminate. Those having compatibility with the heat-adhesive resin layer provided on the inner layer are preferred.
- this protective sheet may be appropriately selected and used depending on the type of the heat-adhesive resin layer provided in the inner layer of the paper container, like the adhesive layer of the laminate.
- the heat-adhesive resin layer exemplified as that which can be used for the adhesive layer that is, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene Polymer, ethylene ⁇ -olefin copolymer, ionomer, ethylene monoacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene propylene copolymer, etc.
- a non-greasy sheet that is more powerful, or a sheet in which these are made into a film.
- the thickness of the heat-adhesive resin layer of this protective sheet is suitably 50 to 220 m.
- the protective sheet When the protective sheet is thermally bonded to the adhesive layer provided on the contents side of the laminate, the protective sheet is naturally peeled off from the adhesive layer provided on the contents side of the laminate. It is necessary to be able to be heat-bonded firmly to the extent that Those having compatibility with the adhesive layer provided on the object side are preferred. Further, the heat-adhesive resin layer provided on the inner layer of the paper container, the adhesive layer formed on the laminate, and the heat-adhesive resin layer formed on the protective sheet are all determined by the contents or required. You can choose the one that best suits your function.
- a laminate including a paper layer When a laminate including a paper layer is simply cut out, an end portion of the paper layer appears in the cutout portion. If the edge comes into contact with the outside of the container, the edge of the paper layer will damage the paper container. In addition, when this end comes into contact with the contents of the container, moisture enters from the end of the paper layer. Therefore, it is preferable to cover the edge of the paper layer with grease.
- the following method can be adopted as a specific method of covering the edge of the paper layer. That is, a laminated body composed of E) layer, Z paper layer, and ZPE layer in polyethylene is prepared by extrusion lamination method.
- the notch in the paper layer bonds the PE layer to the PE layer on the opposite side of the paper layer. After that, by cutting out the PE layer ZPE layer in the notch portion of the paper layer so that the end portion of the paper layer does not appear, a window portion where the end portion of the paper layer is not exposed can be produced.
- the paper layer edge can also be obtained by providing a notch in the paper in advance and applying hot melt adhesive to the paper surface by the gravure method so that the paper layer edge does not appear. It is possible to produce a window portion that is not exposed.
- the retort paper container in the present invention includes at least a paper layer, a heat-resistant polyolefin layer, and a gas nolia layer.
- the gas nolia layer is a specific gas noria layer.
- the type of paper container is not particularly limited! /, For example, single-board type gobel top type, brick type, rectangular parallelepiped type, conical type paper container, cup type paper container, Examples include spiral-type paper containers and insert-molded paper containers.
- the paper layer constituting the laminate of the present invention is a layer that maintains shape retention when formed into a container.
- the resin used in the heat-resistant polyolefin layer constituting the laminate of the present invention has a linear low Powers including density polyethylene-based resin, high-density polyethylene-based resin, and polypropylene-based resin.
- Polypropylene is preferably used because of its high heat resistance.
- Polypropylene-based resin has a melting point of 100 ° C or higher, preferably 120 ° C or higher, more preferably 130 ° C or higher.
- the polypropylene resin may be a polypropylene homopolymer!
- It may be a random copolymer or block copolymer obtained by copolymerizing propylene and one or more other monomers, or a polymer obtained by graft polymerization of one or more other monomers to polypropylene.
- the stereoregularity of polypropylene may be any of isotactic, atactic, syndiotactic and the like.
- the monomers that may be copolymerized with propylene include ethylene, 1-butene, 1-pentane, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dode. Examples include decene, 3-methyl-1-butene, 3-methyl-1 pentene, 4-methyl-1 pentene, 2,2,4 trimethylpentene, and the like.
- the monomer may be graft polymerized to polypropylene, and examples of the monomer include acrylic acid, methacrylic acid, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, jetyl maleate, and maleic acid.
- a laminate Z including a heat-resistant polyolefin layer Z paper layer Z a heat-resistant polyolefin layer Z a gas-noble layer is used.
- the heat-resistant polyolefin layer is composed of a misalignment of a biaxially stretched heat-resistant polyolefin film or a non-stretched heat-resistant polyolefin film, but from the viewpoint of ease of molding, the laminate is composed of It is preferable that both the polyolefin layer and the unstretched polypropylene film are constructed.
- the outermost layer and the polypropylene layer disposed in the innermost layer of the laminate are preferably composed of an unstretched polypropylene film.
- the laminate including the gas barrier layer is a laminate composed of a gas barrier layer, a Z base layer, a Z gas barrier layer, a gas barrier layer, a Z base layer, and a base layer, and is appropriately bonded between the layers.
- a layer can be provided.
- the base material (film) constituting the base material layer This is described later.
- an unstretched heat-resistant polyolefin film or a stretched heat-resistant polyolefin film prepared in advance is used as a film constituting another layer and a known dry lamination method
- a method of laminating by a wet lamination method, a hot melt lamination method or the like, or a method of forming a heat-resistant polyolefin layer on a film constituting another layer by a well-known die extrusion method, etc. can be adopted.
- an adhesive layer can be disposed between the heat-resistant polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coat agent, an adhesive, an adhesive resin, or the like.
- the thickness of the heat-resistant polyolefin layer is preferably in the range of 10 to 200 m, more preferably in the range of 20 to 150 m, from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc. preferable.
- the vacuum insulator in which the core material is packaged with a packaging material having at least a gas barrier laminate, and the space in the packaging material is in a vacuum state.
- the gas-conductive laminate is a gas-nore laminate including a base material and a gas-nore layer laminated on at least one surface of the base material, and the gas barrier layer is selected from a carboxyl group and a carboxylic anhydride base force. It comprises a composition comprising a polymer containing at least one functional group, wherein at least a part of the COO group contained in the at least one functional group is neutralized with a metal ion having a valence of 2 or more. It is a vacuum insulator.
- the vacuum heat insulating body of the present invention is a vacuum heat insulating body comprising a core material and a packaging material, and a space in the packaging material is in a vacuum state, and the packaging material is a specific gas barrier layer, more specifically.
- a composition force including a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group, and at least a part of the COO group contained in the at least one functional group is a metal having a valence of 2 or more. It has a gas noble layer neutralized with ions.
- this specific gas layer includes the gas layer of the present invention, the base material, and the gas barrier layer of the present invention laminated on at least one surface of the base material.
- the laminate may be referred to as a gas barrier laminate of the present invention.
- the gas nore layer of the present invention and the gas nore laminate of the present invention will be described in detail separately.
- the gas nore layer of the present invention has high gas nore property and excellent flexibility. It exhibits stable gas barrier performance without being affected by impacts during its manufacture or handling. Also, when used in combination with a metal or metal oxide vapor deposition layer, the vapor deposition layer is protected to prevent the occurrence of defects such as pinholes.
- the vacuum heat insulating body of the present invention exhibits a stable and high heat insulating performance.
- the structure of the packaging material constituting the vacuum heat insulating body of the present invention is not limited as long as the gas barrier laminate of the present invention is included, and the force selected according to the purpose of use of the vacuum heat insulating body and the manufacturing method.
- a laminate comprising the gas barrier laminate of the present invention as a packaging material by heat sealing can be used.
- this laminate including the gas barrier laminate of the present invention may be abbreviated as laminate (I).
- the laminate (I) may have at least a gasnolia laminate, but suitable examples will be described below.
- the layer structure of the laminate (I) including the gas nolia laminate is as follows: gas nolia laminate layer Z polyolefin layer (hereinafter referred to as PO layer), gas noria laminate layer Z gas nolia resin layer ZPO layer, gas noria Laminate layer Z Polyamide layer ZPO layer, Polyamide layer z Gas nore laminate layer ZPO layer, Gas nore laminate layer z Polyamide layer Z Gas noreliable resin layer ZPO layer, Polyamide layer z Gas barrier laminate Z gas barrier resin layer ZPO layer, gas barrier laminate layer, polyester layer, eaves layer, polyester layer, gas barrier laminate layer ZPO layer, gas nore laminate layer ⁇ polyester layer ⁇ gas nore oleoresin layer o layer, polyester layer Z gas barrier property Laminate Z Gas barrier resin layer ZPO layer, PO layer Z Gas nore laminate layer Z Polyolefin layer (hereinafter PO layer), PO layer Z Gas nore laminate layer
- the polyolefin (PO) layer includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene acetate butyl copolymer, ethylene ⁇ -olefin composite weight.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a high-density polyethylene, a resin having a polypropylene strength, or a sheet made of these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. Although these polyolefin layers may be stretched or unstretched, they may be displaced. However, from the viewpoint of heat seal strength, it is preferable that the heel layer disposed in the innermost layer of the laminate (I) is unstretched.
- the eaves layer disposed in the innermost layer of the laminate is composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene, and is most preferably preferable.
- the gas-nozzle resin layer there can be used an ethylene butyl alcohol copolymer, a resin having a polyvinylidene chloride strength, or a sheet obtained by forming a film thereof. It is preferably composed of a stretched ethylene butyl alcohol copolymer.
- a vapor deposition layer made of a metal oxide such as a metal such as aluminum, aluminum oxide, or silicon oxide may be provided on at least one surface of the gas nobulous resin layer. As a vapor deposition method for metals and metal oxides, the same method as described later can be used.
- polyester layer and polyamide layer the polyester layer and polyamide layer described in the explanation of the gas barrier laminate described later can be used.
- an oxygen absorbent such as an unsaturated fatty acid, a water adsorbent such as synthetic zeolite, silica powder, alumina powder, lithium hydroxide powder, or barium hydroxide powder may be used. These may contain an oxygen absorbent and a moisture absorbent in each layer of the laminate (I), or may be used in combination with a core material. It can also be used as an alternative to the core material.
- a method for forming a polyolefin (PO) layer, a polyester layer, and a polyamide layer a non-stretched polyolefin film, a stretched polyolefin film, a non-stretched polyester film, a stretched polyester film, a non-stretched polyamide film
- Other layers can be formed by pasting the stretched polyamide film and the film constituting the other layer with the known dry lamination method, wet lamination method, hot melt lamination method, etc., or with the well-known T-die extrusion method.
- a method of forming a polyolefin layer, a polyester layer, or a polyamide layer on the film constituting the film can be employed.
- an adhesive layer can be disposed between the respective layers as necessary.
- the adhesive layer is formed using an anchor coat agent, an adhesive, an adhesive resin, or the like.
- the core material used in the vacuum heat insulating body of the present invention is not particularly limited as long as it has a heat insulating property, but pearlite powder, silica powder, precipitated silica powder, diatomaceous earth, calcium silicate, Examples thereof include continuous foams such as glass wool, rock wool, styrene foam and urethane foam. Further, a hollow container made of an inorganic material or a hard cam structure may be used as a core material.
- the space in the packaging material is in a vacuum state.
- the vacuum state here does not necessarily mean an absolute vacuum state, but indicates that the pressure in the space inside the packaging material is sufficiently lower than the atmospheric pressure.
- the internal pressure is a force determined by the required performance and ease of manufacture. Usually, it is 2 kPa (about 15 Torr) or less to achieve thermal insulation performance.
- the internal pressure of the packaging material is preferably 20 OPa (about 1.5 Torr) or less, more preferably 20 Pa or less. More preferably, it is as follows.
- the vacuum heat insulating body of the present invention can be manufactured by a conventional method. It can be formed in any shape and size according to the purpose of use. Examples of manufacturing methods include For example, two laminates (I), which will be described in detail later, are stacked so that each heat seal layer is on the inside of the packaging material, heat-sealing any three sides, filling the core material, and then inside the packaging material The part can be made in a vacuum state and the last side can be heat sealed.
- fold one laminating body (I) so that the heat seal layer is inside the packaging material, heat-seal any two sides, fill the core material, evacuate the packaging material, and finally It can be manufactured by heat-sealing the sides, and the core material is sandwiched between two laminates (I) or one laminate (I), leaving the vacuum exhaust port at the periphery. It can also be manufactured by heat-sealing and evacuating, and then heat-sealing the vacuum exhaust port.
- Another aspect of the present invention is an infusion nog that also has a laminate strength having at least a gas nore laminate, wherein the gas nore laminate is a base material and a gas nore laminated on at least one surface of the base member.
- a gas-containing laminate comprising a layer containing a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group, wherein the at least one This infusion bag is characterized in that at least a part of one COO group contained in a functional group is neutralized with a metal ion having a valence of 2 or more.
- an oxygen barrier property is imparted to the infusion bag body, and double packaging with an exterior material is unnecessary, and the components of the infusion bag are dissolved in the infusion. It is possible to provide an infusion bag without worry. Furthermore, it has extremely good oxygen noria properties, can be heat-sterilized at high temperatures, and has a high oxygen barrier property even after high-temperature heat sterilization. Before heat sterilization, during heat sterilization, after heat sterilization, after transportation, and after storage It is possible to provide an infusion bag that can prevent alteration of a filled liquid medicine due to oxygen.
- the infusion bag of the present invention can be produced by a conventional bag-making method. It can be formed in any shape and size according to the purpose of use.
- the bag making method include a single laminate comprising a gas nore laminate of the present invention (hereinafter sometimes referred to as a gas barrier laminate (I)), or a gas nore laminate, which will be described in detail later.
- a method of forming a multilayer laminate containing (I) and making a bag from the laminate can be employed.
- the laminated body is overlaid, and after sealing the periphery into a predetermined shape to form a bag, the plug member obtained by injection molding of polyethylene or polypropylene, etc. May be attached by heat sealing.
- the configuration of the laminate forming the infusion bag of the present invention is not limited as long as it includes the gas barrier laminate (I).
- Gas nore laminate (I) A single laminate or a multi-layer laminate including the gas barrier laminate (I) may be used.
- the layer structure of the multilayer laminate including the gas barrier laminate (I) is as follows: gas no laminate (I) layer Z polyolefin layer (hereinafter referred to as Po layer), po layer Z gas barrier laminate (I) layer, po Layer Z gas barrier laminate (I) Layer ZPO layer, gas nore laminate (I) Layer Z polyamide layer ZPO layer, polyamide layer Z gas nore laminate (I) ZPO layer, PO layer Z gas barrier laminate (I) Layer Z Polyamide Layer ZPO Layer, PO Layer Z Polyamide Layer Z Gas Barrier Laminate (I) ZPO Layer, Gas Barrier Laminate ( ⁇ ) Layer Z Thermoplastic Elastomer Layer, Thermoplastic Elastomer Layer Z Gas Norality Layer Body (I) Layer, Thermoplastic Elastomer Layer Z Gas Nor
- the polyolefin (PO) layer includes a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear (linear) low density polyethylene, a polypropylene, an ethylene acetate butyl copolymer, an ethylene ⁇ -olefin composite.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low density polyethylene, a linear (linear) low density polyethylene, or a resin or polypropylene that has polypropylene strength.
- This is a sheet made of these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the viewpoint of ease of molding, heat resistance, etc., the above laminate is constructed!
- the misaligned PO layer is also unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. It is more preferable to use unstretched linear (linear) low density polyethylene or unstretched polypropylene.
- the PO layer disposed in the innermost layer of the laminate is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- thermoplastic elastomer is one of a thermoplastic polyurethane, a thermoplastic styrene elastomer, a thermoplastic amide elastomer, a thermoplastic ester elastomer, or a resin that has more power.
- a sheet in which these are formed can be used.
- a method for forming a polyolefin (PO) layer and a thermoplastic elastomer layer a previously prepared unstretched polyolefin film, stretched polyolefin film, unstretched thermoplastic elastomer film, stretched thermoplastic elastomer film and other The film constituting the layer and the film constituting the other layer by the well-known dry lamination method, wet lamination method, hot melt lamination method, etc., or the well-known T-die extrusion method, etc.
- a method of forming a polyolefin layer, a thermoplastic elastomer, or the like can be employed.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive grease, or the like.
- the layer is a specific gas noble layer.
- the gas barrier laminate including such a specific gas nore layer may be referred to as the gas nore laminate of the present invention.
- FIG. 1 Another aspect of the present invention is a container lid member having at least a gas- noble laminate, wherein the gas-nozzle laminate is a base material and a gas node laminated on at least one surface of the base material.
- a gas-noir laminate including a rear layer, wherein the gas-noria layer includes a carboxyl group and a And at least one of the coo groups contained in the at least one functional group is divalent or higher.
- the container lid is characterized by being neutralized with metal ions.
- the lid material of the present invention has a recess-shaped storage portion for storing contents by vacuum forming, pressure forming, or the like and a flange portion extending outwardly from the opening end of the storage portion in a flange shape.
- a joining method a joining method by heat sealing is preferable, and can be mentioned as a joining method.
- the configuration of the lid member of the present invention is not limited as long as it includes the gas noble laminate of the present invention (which may be hereinafter referred to as gas noria laminate (I)).
- the gas barrier laminate (I) may be a single laminate, or a multilayer laminate including the gas barrier laminate (I).
- the layer structure of the multilayer laminate including the gas barrier laminate (I) the gas laminate laminate (I) layer Z polyolefin layer (hereinafter referred to as PO layer), gas barrier laminate ( I) Layer Z Polyamide layer ZPO layer, Polyamide layer Z Gas barrier laminate (I) Layer ZP
- the polyolefin (PO) layer includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene acetate butyl copolymer, ethylene ⁇ -olefin composite.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a resin having a polypropylene strength, or a sheet formed from these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the standpoint of ease of molding and heat resistance, the above laminate is constructed!
- the misaligned heel layer is also unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. It is more preferable to use unstretched linear (linear) low density polyethylene or unstretched polypropylene.
- the eaves layer disposed in the innermost layer of the lid member is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. .
- the thickness of the polyamide layer is not particularly limited, but is preferably in the range of 10 to 200 m from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc. 20 ⁇ 15 0
- polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide MXD6 is one type or more of a type of resin, or a sheet in which these are formed into a film. be able to. These polyamide layers may be either stretched or unstretched.
- a preferable polyamide layer is a sheet obtained by forming polyamide 6 and polyamide 66 into a film and stretching. The thickness of the polyamide layer is particularly limited Although it is not a thing, it is preferable that it is in the range of 5 to 200 m from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc. 5-: LOO
- Examples of paper used for the paper layer include kraft paper, high-quality paper, imitation paper, darashin paper, parchment paper, synthetic paper, white paperboard, marble board, milk carton base paper, cup base paper, and ivory paper. Can be used.
- a method for forming a polyolefin (PO) layer and a polyamide layer a non-stretched polyolefin film, a stretched polyolefin film, a non-stretched polyamide film, a stretched polyamide film and a film constituting another layer, which have been facilitated in advance, are well known.
- a method of laminating by a dry lamination method, a wet lamination method, a hot melt lamination method, etc., or a method of forming a PO layer or a polyamide layer on a film constituting another layer by a well-known T-die extrusion method, etc. Etc. can be adopted.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive grease, or the like.
- Another aspect of the present invention is a laminated tube container having at least a gas- noble laminate, wherein the gas-nozzle laminate is a base material and a gas nozzle laminated on at least one surface of the base material.
- a gas-nootropic laminate comprising a layer, wherein the gas barrier layer comprises a polymer containing a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride base, and the at least one functional
- the laminating tube container is characterized in that at least a part of the COO group contained in the group is neutralized with a divalent or higher metal ion.
- the conventional laminated tube container is excellent from the viewpoint of environmental 'disposal' and the like, has a variety of container designs, has resistance to retort sterilization, and is conventional. It is possible to provide a laminated tube container that is superior in oxygen-relative properties and has no deterioration in oxygen-nore property even when the laminated tube container is squeezed. The contents packed in a laminated tube container are consumed little by little, and the consumption period is often long.
- the laminated tube container of the present invention is particularly suitable for pharmaceuticals, cosmetics, foods and the like whose contents are susceptible to oxygen degradation.
- the laminated tube container of the present invention comprises a base material and a specific gas barrier layer (hereinafter referred to as a gas barrier layer used in the present invention) laminated on at least one surface of the base material.
- a gas barrier layer used in the present invention laminated on at least one surface of the base material.
- a gas-nolia laminate (I) a specific gas barrier layer laminate (hereinafter, sometimes referred to as a gas-nolia laminate (I)
- a barrel portion formed into a cylindrical shape from a laminate and a threaded mouth portion formed from a thermoplastic resin by an injection molding method or the like.
- Consists of a shoulder and a cap For example, a laminate having a gas barrier laminate is bent into a cylindrical shape, and both end edges in the longitudinal direction are overlapped, and the overlapped portions are heat-welded by high frequency and bonded to produce a cylindrical body.
- the laminate tube container of the present invention is a trunk formed into a cylindrical shape from a laminate having the gas nore laminate (hereinafter sometimes referred to as gas barrier laminate (I)) used in the present invention. And a shoulder portion having a threaded mouth portion formed by an injection molding method or the like from thermoplastic resin and a cap portion cover.
- gas barrier laminate a laminate having a gas barrier laminate is bent into a cylindrical shape, and both end edges in the longitudinal direction are overlapped, and the overlapped portions are heated and welded at a high frequency to produce a cylindrical barrel.
- the cylindrical body mouth and shoulder are bonded by placing shoulder parts on the cylindrical body mouth and heat welding with high frequency welding or a gas burner. It is possible to employ a method in which a thermoplastic resin is melt-injected and compression-molded at the mouth of the fixed cylindrical body.
- a laminated tube container is manufactured by attaching a cap part formed by injection molding to the threaded mouth part, subsequently filling the contents of the butt part force, and then joining the butt part by high-temperature heat welding or the like. be able to.
- the configuration of the laminate used in the present invention is not particularly limited as long as it includes the gas nore laminate (I) including the gas barrier layer used in the present invention, but the inside of the laminate tube container is not limited.
- the layer to be used is preferably a polyolefin layer (hereinafter sometimes referred to as PO layer) in terms of the point of heat sealability.
- PO layer polyolefin layer
- the configuration of the laminate used in the present invention is such that, for example, when used as a laminate container, the PO layer is directed from the outer layer to the inner layer.
- Z gas barrier laminate (I) ZPO layer po layer Z pigment-containing PO layer ZPO layer Z gas barrier laminate (I) ZPO layer, PO layer ⁇ polyamide layer ⁇ gas barrier laminate (I) ZPO layer, PO layer Z pigment-containing PO layer ZPO layer z polyamide layer Z gas barrier laminate (I) ZPO layer, po layer
- Z gas barrier laminate Z ethylene monobutyl alcohol copolymer layer (EVOH layer) ZPO layer, PO layer Z pigment-containing PO layer ZPO layer Z gas barrier laminate (I) / EVOH layer ZPO layer, PO layer Z polyamide layer Z gas barrier laminate (I) ZEVOH layer ZPO layer, PO layer Z pigment-containing PO layer ZPO layer Z polyamide layer Z gas barrier laminate (i) ZEVOH layer Z PO layer be able to.
- Particularly preferred laminate structures include PO layer Z gas barrier laminate (I) ZPO layer, PO layer Z pigment-containing PO layer ZPO layer Z gas barrier laminate (I) ZPO layer.
- An adhesive layer can be appropriately provided between the layers.
- the polyolefin layer, the pigment-containing polyolefin layer, the polyamide layer, and the ⁇ layer will be described in detail.
- the polyolefin (PO) layer includes low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene acetate butyl copolymer, ethylene ⁇ -olefin composite weight.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a resin having a polypropylene strength, or a sheet formed from these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the standpoint of ease of molding and heat resistance, the above laminate is constructed!
- the misaligned heel layer is also unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. It is more preferable to use unstretched linear (linear) low density polyethylene or unstretched polypropylene.
- the eaves layer disposed in the innermost layer of the laminate is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- the thickness of the heel layer is not particularly limited, but is preferably in the range of 10 to 300 / ⁇ ⁇ from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., and 50 to 200 111 I like the range of 1 ⁇ 0 [0107]
- polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide MXD6 is one type or more of a type of resin, or a sheet in which these are formed into a film. be able to.
- These polyamide layers may be either stretched or unstretched.
- a preferred polyamide layer is a sheet obtained by film-forming and stretching polyamide 6 and polyamide 66.
- the thickness of the polyamide layer is not particularly limited, but is preferably in the range of 5 to 200 m from the viewpoints of mechanical toughness, impact resistance, puncture resistance, etc. 5: LOO m More preferably, it is in the range.
- EVOH ethylene butyl alcohol copolymer
- ethylene-vinyl alcohol copolymer two or more kinds of resins having different ethylene contents, or a sheet obtained by filming these. It can.
- These EVOH layers can be either stretched or unstretched or misaligned. Desirable ⁇
- the EVOH layer is a sheet obtained by forming a film of an ethylene butadiene alcohol resin and stretching it.
- the thickness of the EVOH layer is not particularly limited, but it is preferably in the range of 5 to 200 / ⁇ ⁇ from the viewpoints of gas resistance, mechanical toughness, impact resistance, puncture resistance, etc. 5: More preferably in the range of LOO / zm.
- Polyolefin (PO) layer, polyamide layer, and EVOH layer can be formed in advance by using an unstretched polyolefin film, stretched polyolefin film, unstretched polyamide film, stretched polyamide film, unstretched EVOH, stretched in advance.
- EVOH film and other layers can be combined with other layers by the well-known dry lamination method, wet lamination method, hot melt lamination method, etc., or the well-known T-die extrusion method.
- a method of forming a PO layer, a polyamide layer, or an EVOH layer on the film to be used can be employed.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive grease, or the like.
- the threaded shoulder and the cap of the laminated tube container of the present invention can be manufactured by a known structure and a known method.
- it can be produced by forming a thermoplastic resin by injection molding or the like.
- the thermoplastic resin include low density polyethylene, Medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, polyolefins such as olefinic elastomers, ethylene mono-alpha olefin copolymers, ionomers, ethylene monoacrylic acid copolymers, ethylene mono Methyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene monopropylene copolymers, etc., and blends of these resins with gas barrier resins such as ethylene acetate butyl copolymer and MXD6 polyamide. Can be used.
- the gas noria laminate in the vacuum packaging bag having at least a gas barrier laminate, has a base material and a gas noria layer laminated on at least one surface of the base material.
- a gas nore laminate comprising the yarn and the polymer containing a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group, wherein the at least one functional group It is a vacuum packaging bag characterized in that at least a part of the COO group contained in is neutralized with a metal ion having a valence of 2 or more.
- a vacuum packaging bag of the present invention By using such a vacuum packaging bag of the present invention, deformation of the packaging bag such as folding, bending, and expansion during vacuum packaging, and expansion and bending of the packaging bag during subsequent heat sterilization treatment can be achieved.
- the vacuum packaging bag of the present invention can confirm the state of the contents and has environmental suitability.
- the configuration of the gas noble laminate used in the present invention is not particularly limited as long as it includes the gas noble layer used in the present invention.
- the layer inside the vacuum packaging bag has a heat sealing property.
- a polyolefin layer hereinafter sometimes referred to as a soot layer
- the substrate is directed from the outer layer to the inner layer, so that the substrate ⁇ gas nolia layer ⁇ layer, ⁇ layer
- the vacuum packaging bag is particularly excellent in gas barrier properties after vacuum packaging and after vacuum packaging Z heat sterilization. Above vacuum package An adhesive layer can be appropriately provided between the layers of the bag.
- the polyolefin layer, polyamide layer and gas barrier layer will be described in detail below.
- the polyolefin (PO) layer includes a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear (linear) low density polyethylene, polypropylene, an ethylene acetate butyl copolymer, an ethylene ⁇ -olefin composite.
- a resin that can be used as one or more resins such as a polymer, an ionomer, an ethylene-acrylic acid copolymer, an ethylene methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer!
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a resin having a polypropylene strength, or a sheet formed from these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the standpoint of ease of molding and heat resistance, the above laminate is constructed!
- the misaligned heel layer is also unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. It is more preferable to use unstretched linear (linear) low density polyethylene or unstretched polypropylene.
- the heel layer disposed in the innermost layer of the packaging bag is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- the thickness of the heel layer is not particularly limited, but is preferably in the range of 10 to 200 m from the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc. 20- More preferably, it is in the range of 150 ⁇ m.
- polyamide layer a sheet in which at least one resin selected from polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide MXD6 resin is formed into a film can be used. . These polyamide layers may be stretched or non-stretched. A preferable polyamide layer is a sheet obtained by stretching polyamide 6 and polyamide 66 in a film and stretching.
- the thickness of the polyamide layer is not particularly limited. 1S From the viewpoint of mechanical toughness, impact resistance, puncture resistance, etc., it is preferably in the range of 5 to 200 m 5: LOO / zm More preferably, it is in the range.
- a vacuum packaging bag having a gas nolia layer as an outermost layer and a polyamide layer inside is compared with a configuration having a conventional polyamide layer.
- the mechanical or mechanical properties are not lowered after retort treatment, and it is preferably used.
- a method for forming a polyolefin (PO) layer and a polyamide layer an unstretched polyolefin film, a stretched polyolefin film, an unstretched polyamide film, a stretched polyamide film and a film constituting another layer, which have been facilitated in advance, are well known.
- a method of laminating by a dry lamination method, a wet lamination method, a hot melt lamination method, etc., or a method of forming a PO layer or a polyamide layer on a film constituting another layer by a well-known T-die extrusion method, etc. Etc. can be adopted.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary.
- the adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive grease, or the like.
- the vacuum packaging bag of the present invention can be produced by a conventional bag-making method. It can be formed in any shape and size according to the purpose of use.
- a bag-making method for example, a method of forming a laminate including a gas nolia layer used in the present invention, which will be described in detail later, and making a bag by using this laminate strength can be employed.
- a bag from a laminate stack the laminate, heat-seal the surrounding three sides, fill the contents, degas the inside of the packaging bag, and heat-seal the last side .
- the gas barrier laminate is laminated on at least one surface of the substrate.
- a gas nore laminate comprising the gas nore layer, wherein the gas nore layer comprises a polymer containing a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride base, and the at least one function Included in the group — COO—
- the body of the bouch has a high oxygen barrier property even after heat sterilization at a high temperature, and has transparency, so that a metal detector can be used.
- the sputt is attached by bending or impact during filling or transportation of the contents. It becomes possible to provide a spout with a spout where the spout pouch main body heat seal part, in particular, the edge part, etc. is not damaged and the noria property is not deteriorated.
- the spouted bouch of the present invention has a base material and a specific gas nolia layer (hereinafter sometimes referred to as a gas noria layer used in the present invention) laminated on at least one surface of the base material. It is composed of a gas barrier laminate (hereinafter sometimes referred to as gas noria laminate (I)).
- gas barrier laminate hereinafter sometimes referred to as gas noria laminate (I)
- the gas barrier laminate is laminated and provided in the state of a packaging bag in which the three surrounding sides are heat-sealed. It is done. In use, after filling the packaging bag, the inside of the packaging bag is evacuated and the last side is heat-sealed.
- the structure of the laminated body forming the spouted bouch of the present invention is not limited as long as it includes a gas nolia layer. However, as a layer inside the spouted bouch, a polyolefin layer ( (Hereinafter sometimes referred to as PO layer).
- the structure of the gas barrier laminate used in the present invention includes, for example, a gas nore layer, a Z base layer, a ZPO layer, and a gas nore layer that are directed from the outer layer to the inner layer when used as a spouted bouch.
- an adhesive layer can be appropriately provided between the layers.
- the polyolefin layer and the thermoplastic elastomer layer will be described in detail below.
- the polyolefin (PO) layer includes a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear (linear) low density polyethylene, a polypropylene, an ethylene acetate butyl copolymer, an ethylene ⁇ -olefin composite. Copolymer, ionomer, ethylene-acrylic acid copolymer, ethylene methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, etc.
- a sheet obtained by filming these can be used.
- These polyolefin layers can be stretched or unstretched or misaligned.
- the polyolefin layer is a low-density polyethylene, a linear (linear) low-density polyethylene, a resin having a polypropylene strength, or a sheet formed from these. More preferably, linear (linear) low density polyethylene and polypropylene are preferred. From the viewpoint of ease of molding, heat resistance, etc., the above laminate is constructed!
- the misaligned PO layer is also unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene. It is more preferable to use unstretched linear (linear) low density polyethylene or unstretched polypropylene.
- the PO layer disposed in the innermost layer of the laminate is preferably composed of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, and unstretched polypropylene.
- Polyolefin (PO) layer and thermoplastic elastomer single layer can be formed by using a previously prepared unstretched polyolefin film, stretched polyolefin film, unstretched thermoplastic elastomer film, stretched thermoplastic elastomer film and other The film constituting the layer and the film constituting the other layer by the well-known dry lamination method, wet lamination method, hot melt lamination method, etc., or the well-known T-die extrusion method, etc. A method of forming a polyolefin layer, a thermoplastic elastomer, or the like can be employed.
- an adhesive layer can be disposed between the polyolefin layer and other layers as necessary. The adhesive layer is formed using an anchor coating agent, an adhesive, an adhesive grease, or the like.
- the gas noble layer of the present invention that is, the gas noble layer contained in the gas noble laminate of the present invention has a composition force including a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride group.
- At least a part of the COO group contained in the at least one functional group is neutralized by a metal ion having a valence of 2 or more, in other words, at least a part of the at least one functional group is a valence of 2 or more. It consists of metal ions and salts.
- the composition constituting the gas noor layer includes a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group.
- the content of the polymer neutralized product in the composition is not particularly limited, and can be, for example, in the range of 25 wt% to 95 wt%.
- the neutralized product of this polymer is a polymer containing at least one functional group selected from a carboxyl group and a carboxylic acid anhydride base (hereinafter sometimes referred to as “carboxylic acid-containing polymer”). It is a polymer obtained by neutralizing at least a part of one functional group with a divalent or higher metal ion.
- the carboxylic acid-containing polymer has two or more carboxyl groups or one or more carboxylic anhydride groups in one molecule of the polymer.
- a polymer containing at least two structural units having at least one carboxyl group such as an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, and an itaconic acid unit in one molecule is used.
- a polymer containing a structural unit having a carboxylic anhydride structure such as an anhydrous maleic acid unit or a phthalic anhydride unit can also be used.
- At least one type of structural unit having at least one carboxyl group and structural unit having a structure of Z or carboxylic anhydride hereinafter sometimes abbreviated as carboxylic acid-containing unit (C)). Two or more types may be included.
- the content of the carboxylic acid-containing unit (C) in the total structural unit of the carboxylic acid-containing polymer is set to 10 mol% or more, a gas barrier that has good gas noriability under high humidity.
- a conductive laminate is obtained.
- the content is more preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 70 mol% or more.
- the carboxylic acid-containing polymer includes both a structural unit containing one or more carboxyl groups and a structural unit having a carboxylic acid anhydride structure, the sum of both is within the above range. Good.
- the structural unit other than the carboxylic acid-containing unit (C) may be included in the carboxylic acid-containing polymer, but is not particularly limited, but includes a methyl acrylate unit, a methyl methacrylate unit, Structural units derived from (meth) acrylic acid esters such as ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units; vinyl formate Units, structural units derived from butyl esters such as butyl acetate units; styrene units, p-styrene sulfonic acid units; olefins such as ethylene units, propylene units and isobutylene units.
- the carboxylic acid-containing polymer contains two or more structural units
- the carboxylic acid-containing polymer is in the form of an alternating copolymer, a random copolymer, a block copolymer, or even It may be in the form of a taper type copolymer.
- carboxylic acid-containing polymer U for example, polyacrylic acid, polymethacrylic acid, poly
- the carboxylic acid-containing polymer may be one kind or a mixture of two or more kinds of polymers.
- at least one polymer selected from polyatallylic acid and polymethacrylic acid may be used.
- Specific examples in the case of containing other structural units described above include ethylene maleic anhydride copolymer, styrene maleic anhydride copolymer, isobutylene maleic anhydride copolymer, ethylene acrylic acid copolymer. And an ethylene ethyl acrylate copolymer.
- the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but the number average molecular weight is 5 because the gas barrier property of the obtained gas-barrier laminate is excellent and the mechanical properties such as drop impact strength are excellent. More preferably, it is 10,000 or more, more preferably 10,000 or more, and further preferably 20,000 or more.
- the upper limit of the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.
- the molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited! /, But the surface appearance such as haze of the gas-nominated laminate and the storage stability of the solution (S) described later
- the molecular weight distribution represented by the ratio of the weight average molecular weight Z number average molecular weight of the carboxylic acid-containing polymer is preferably in the range of 1 to 6 in the range of 1 to 5. More preferably, it is more preferably in the range of 1-4.
- the polymer constituting the gas nore layer of the gas nore laminate of the present invention has at least one functional group (hereinafter referred to as "functional group")) selected from the carboxyl group and carboxylic anhydride base strength of the carboxylic acid-containing polymer.
- a functional group hereinafter referred to as "functional group”
- the polymer contains a carboxyl group neutralized with a divalent or higher metal ion.
- the polymer constituting the gas barrier layer is neutralized with, for example, 10 mol% or more (for example, 15 mol% or more) of a COO group contained in the functional group (F) and a metal ion having a valence of 2 or more.
- Carboxylic anhydride groups are considered to contain two —COO groups. That is, when there are a moles of carboxyl groups and b moles of carboxylic acid anhydride groups, the total COO groups contained in it are (a + 2b) moles.
- the proportion of the COO group contained in the functional group (F) that is neutralized with a metal ion having a valence of 2 or more is preferably 20 mol% or more, more preferably 30 mol% or more, and The amount is preferably 40 mol% or more, particularly preferably 50 mol% or more (for example, 60 mol% or more).
- the upper limit of the proportion of COO groups neutralized with divalent or higher-valent metal ions is not particularly limited, but can be, for example, 95 mol% or less.
- the gas barrier laminate of the present invention can be subjected to a dry condition and a high humidity condition. Both show good gas noria properties.
- the degree of neutralization (ionization degree) of the functional group (F) is determined by the force of measuring the infrared absorption spectrum of the gas barrier laminate by the ATR (total reflection measurement) method, It can be obtained by striking the layer and measuring its infrared absorption spectrum by the KBr method.
- the ratio of the maximum absorbance force in each range can also be obtained, and the ionization degree of the polymer constituting the gas nore layer in the gas nore laminate can be calculated using a calibration curve prepared in advance. it can.
- a calibration curve can be created by measuring infrared absorption spectra of a plurality of standard samples having different degrees of neutralization.
- the metal ion neutralizing the functional group (F) is divalent or higher. If the functional group (F) is not neutralized or is neutralized only by the monovalent ions described below, A laminated body having gas noriality cannot be obtained. However, if the functional group (F) is neutralized with a small amount of monovalent ions (cations) in addition to divalent or higher metal ions, the haze of the gas barrier laminate is reduced and the surface Appearance is improved. Thus, the present invention includes the case where the functional group (F) of the carboxylic acid-containing polymer is neutralized with both a divalent or higher metal ion and a monovalent ion.
- divalent or higher metal ions examples include calcium ion, magnesium ion, divalent iron ion, trivalent iron ion, zinc ion, divalent copper ion, lead ion, divalent mercury ion, and norium ion.
- at least one ion selected from calcium ion, magnesium ion, and zinc ion force may be used as the divalent or higher metal ion.
- the composition constituting the gas nore layer in the gas nore laminate of the present invention is based on the carboxylic acid-containing polymer and the neutralized product thereof, and is at least one selected from a halogen atom and an alkoxy group.
- it contains a hydrolysis condensate of at least one compound (L) containing a metal atom to which a characteristic group (atomic group) is bonded.
- the compound (L) at least one of the compounds (A) and Z or the compound (B) described below can be applied.
- the compound (A) and the compound (B) will be described.
- Compound (A) is at least one compound represented by the following formula (I).
- M 1 is Si ⁇ Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W Represents an atom selected from La, Nd.
- M 1 is preferably Si, ⁇ 1, ⁇ or Zr, and particularly preferably Si.
- R 1 is an alkyl group such as a methyl group, an ethyl group, an n propyl group, an iso propyl group, an n butyl group, or a t butyl group, preferably a methyl group or an ethyl group. .
- X 1 represents a halogen atom.
- halogen atom represented by X 1 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
- Z 1 represents an alkyl group substituted with a functional group having reactivity with a carboxyl group.
- examples of the functional group having reactivity with a carboxyl group include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, or a force epoxy group, An amino group, mercapto group, isocyanate group, ureido group, or halogen atom is preferred.
- Examples of the alkyl group substituted with such a functional group include those mentioned above.
- m is equal to the valence of the metal element M 1 .
- n represents an integer of 0 to (! N— 1).
- k represents an integer of 0 to (m—1), and 1 ⁇ n + k ⁇ (m—1).
- the compound (A) include ⁇ -glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and cyclopropyl propyl. Trimethoxysilane , ⁇ bromopropyltrimethoxysilane , ⁇ mercaptopropyltrimethoxysilane , ⁇ - isocyanatepropyltrimethoxysilane , ⁇ -ureidopropyltrimethoxysilane, etc.
- an ethoxy group, ⁇ -propoxy group, isopropoxy group, n-butoxy group, and t-butoxy group may be used as an alkoxy group or a chlorine compound.
- the methoxy group of these compounds can be substituted with ethoxy, n-propoxy, isopropoxy , N-butoxy group, t-butoxy group and the like, which are alkoxy groups or chlorine groups, may be used.
- Preferred examples of the compound (A) include y-glycidoxypropyltrimethoxysilane, y- dalicidoxypropyltriethoxysilane , ⁇ -black propyltrimethoxysilane , and ⁇ -black propyltriethoxysilane.
- the compound) is at least one compound represented by the following chemical formula (II).
- M 2 is Si ⁇ Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W
- R 2 is a force representing an alkyl group such as a methyl group, an ethyl group, an n propyl group, an iso propyl group, an n butyl group, or a t butyl group, preferably a methyl group or an ethyl group.
- X 2 represents a halogen atom.
- the halogen atom represented by X 2 include a chlorine atom, an iodine atom, and an iodine atom, and a chlorine atom is preferred.
- R 3 represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. Examples of the alkyl group represented by R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-octyl group.
- Examples of the aralkyl group represented by R 3 include a benzyl group, a phenethyl group, and a trityl group.
- Examples of the aryl group represented by R 3 include a phenol group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group.
- examples of the alkenyl group represented by R 3 include a bur group and a allyl group.
- p is equal to the valence of the metal element M 2.
- q is ⁇ Represents an integer of p.
- r. ⁇ Represents an integer of p, l ⁇ q + r ⁇ p.
- M 1 and M 2 may be the same or different.
- R 1 and R 2 may be the same or different.
- Specific examples of the compound (B) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, etyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethylsilane.
- Silicon alkoxides such as ethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorojetoxysilane, trichlorosilane methoxysilane, and trichlorosilane ethoxysilane; halogens such as vinyltrichlorosilane, tetrachlorosilane, and tetrabromosilane Silane; Tetramethoxytitanium, Tetraethoxytitanium, Tetraisopropoxytitanium, Methyltriisopropoxytitanium and other alkoxytitanium compounds; Tan; trimethoxy aluminum Yuumu, triethoxy aluminum, triisopropoxy aluminum, methyl diisopropoxy Alkoxyaluminum compounds such as silicon aluminum, tributoxyaluminum and diethoxyaluminum chloride; alkoxyzirconium compounds such as
- the composition constituting the gas barrier layer of the gas barrier laminate of the present invention preferably contains a hydrolytic condensate of compound (L).
- a hydrolytic condensate of compound (L) By hydrolyzing the compound (L), at least a part of the halogen and alkoxy groups of the compound (L) is substituted with hydroxyl groups. Furthermore, the hydrolyzate condenses to form a compound in which metal elements are bonded through oxygen. When this condensation is repeated, the compound is substantially regarded as a metal oxide.
- the hydrolysis condensate of compound (L) contained in the gas barrier layer of the gas barrier laminate preferably has a degree of condensation P defined below of 65 to 99%, preferably 70 to 99%. More preferably, it is more preferably 75 to 99%.
- the degree of condensation P (%) in the hydrolytic condensate of compound (L) is calculated as follows.
- the total number of alkoxy groups and halogen atoms in one molecule of compound (L) is a, and the total of condensed alkoxy groups and halogen atoms in the hydrolysis condensate of compound (L) is i (pieces)
- i is an integer (including 1 and a) of l to a ⁇ (i / a ) Calculate Xyi ⁇ and add them. That is, the degree of condensation P (%) is defined by the following equation.
- the above yi value can be measured by solid NMR (DDZMAS method) etc. for the hydrolysis condensate of compound (L) in the gas barrier layer.
- the hydrolysis-condensation product includes compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially It can be produced by using, for example, a method used in a known sol-gel method, starting from a material that has been hydrolyzed and condensed, a compound (L) that has been completely hydrolyzed and partly condensed, or a combination thereof. . These raw materials may be produced by a known method, or commercially available ones may be used.
- a condensate obtained by hydrolysis and condensation of about 2 to 10 molecules can be used as a raw material.
- tetramethoxysilane hydrolyzed and condensed to form a 2-10 mer linear condensate can be used as a raw material.
- the number of molecules condensed in the hydrolytic condensate of compound (L) in the composition constituting the gas barrier layer of the gas barrier laminate is determined by the amount of water, the type of catalyst, It can be controlled by the concentration, the temperature at which hydrolytic condensation is performed, and the like.
- the production method of the hydrolyzed condensate of compound (L) is not particularly limited! /, But in a typical example of the sol-gel method, by adding water, an acid and an alcohol to the above-mentioned raw material, Perform hydrolysis and condensation.
- the compound (L) may be described as a metal alkoxide (a compound containing a metal to which an alkoxy group is bonded). Instead of using a metal alkoxide, a compound containing a metal to which a halogen is bonded is used. Moh.
- the compound (L) can be at least one of the compounds (A) and Z or the compound (B).
- the compound (L) contains only the compound (A) or contains both the compound (A) and the compound (B), it is preferable because the gas noirality of the gas noble laminate is improved.
- the compound (L) substantially serves as both the compound (A) and the compound (B), and the molar ratio of the compound (A) Z compound (B) is 0.5 / 99.5 to 40Z60. More preferably, it is in the range.
- the gas barrier laminate has excellent properties such as gas barrier properties, mechanical properties such as tensile strength and elongation, appearance, and handleability.
- the molar ratio of compound ( ⁇ ) ⁇ compound ( ⁇ ) is more preferably in the range of 3 ⁇ 97 to 40 ⁇ 60, and even more preferably in the range of 5 ⁇ 95 to 30 ⁇ 70.
- the content of the inorganic component in the composition constituting the gas barrier layer is preferably in the range of 5 to 50% by weight from the viewpoint of improving the gas noria property of the gas noria laminate. This content is more preferably in the range of 10 to 45% by weight, still more preferably in the range of 15 to 40% by weight.
- the content of the inorganic component in the composition can be calculated from the weight force of the raw material used when preparing the composition.
- compound (L) compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed, compound (L)
- the weight of the metal oxide is calculated assuming that the product is completely hydrolyzed and partly condensed, or a combination of these is completely hydrolyzed and condensed into a metal oxide. To do.
- the calculated content of the inorganic component is calculated by regarding the calculated weight of the metal oxide as the weight of the inorganic component in the composition.
- an inorganic additive such as a metal salt, metal complex, or metal oxide as described later
- the weight of the added inorganic additive is added to the weight of the inorganic component as it is. More specifically describing the calculation of the weight of the metal oxide, the compound represented by the chemical formula (I) (
- the part of (q + r) / 2 is a metal oxide.
- the composition constituting the gas barrier layer may be carbonate, hydrochloride, nitrate, bicarbonate, sulfate, hydrogensulfate, phosphate within the range not impairing the effects of the present invention as desired.
- Inorganic acid metal salts such as borate and aluminate; organic acid metal salts such as oxalate, acetate, tartrate and stearate; Metal complexes, cyclopentagel metal complexes such as titanocene, metal complexes such as cyan metal complexes; layered clay compounds, crosslinking agents, polyalcohols or other polymer compounds, plasticizers, antioxidants, UV absorption May contain chemicals and flame retardants.
- composition constituting the gas nolia layer is a fine powder of metal oxide produced by hydrolyzing and condensing the above metal alkoxide in a wet manner; Metal oxide fine powder prepared by decomposition, condensation or combustion; silica fine powder prepared by water glass, etc. may be contained.
- composition constituting the gas barrier layer in the gas barrier laminate of the present invention contains polyalcohols, the surface appearance of the gas nore laminate is improved. More specifically, the inclusion of polyalcohols makes it difficult for cracks to occur in the gas noble layer during the production of the gas barrier laminate, and a gas noble laminate having a good surface appearance can be obtained.
- Such polyalcohols used in the present invention are compounds having at least two or more hydroxyl groups in the molecule, and include from low molecular weight compounds to high molecular weight compounds. Preference is given to polybulle alcohol, polyacetate partial saponification products, ethylene-butalcohol copolymer, polyethylene glycol, polyhydroxyethyl (meth) ate, polysaccharides such as starch, polysaccharides such as starch High molecular weight compounds such as polysaccharide derivatives.
- the amount of the polyalcohol used is preferably such that the weight ratio of the carboxylic acid-containing polymer Z polyalcohol is in the range of 10Z90 to 99.5 / 0.5.
- the weight ratio is more preferably in the range of 30Z70 to 99Zl, further preferably 50Z50 to 99Zl, and most preferably 70 to 30 to 982.
- the gas barrier layer of the present invention comprises a neutralized product of a carboxyl group-containing polymer and preferably a hydrolysis condensate of the above-described compound (L) on at least one surface of the base film.
- a gas barrier layer made of a material is formed. This gas barrier layer may be formed on only one surface of the substrate, or may be formed on both surfaces.
- a laminate in which gas barrier layers are formed on both sides of the substrate has the advantage that post-processing such as laminating other films is effective.
- the thickness of the gas barrier layer is not particularly limited, but is preferably in the range of 0.1 m to 100 ⁇ m. If the thickness is less than 0.1 m, the gas barrier property of the gas barrier laminate may be insufficient. On the other hand, if it is thicker than 100 / zm, cracks may easily occur in the gas nore layer during heating, transportation and use of the gas nore laminate. More preferably, the thickness of the gas barrier layer is in the range of 0.1 m to 50 ⁇ m, 0.1 m to 20 ⁇ m. More preferably, it is the range.
- the gas-noreal laminate of the present invention may further include an adhesive layer (T 2) disposed between the base material and the gas barrier layer.
- an adhesive layer (T 2) disposed between the base material and the gas barrier layer.
- the adhesive layer (T) made of an adhesive resin can be formed by treating the surface of the substrate with a known anchor coating agent or applying a known adhesive to the surface of the substrate.
- the laminate of the present invention may include a layer (hereinafter also referred to as "inorganic layer") that also has an inorganic strength between the base material and the gas nolia layer.
- the inorganic layer can be formed of an inorganic material such as an inorganic oxide.
- the inorganic layer can be formed by a vapor deposition method such as a vapor deposition method.
- the inorganic substance constituting the inorganic layer is preferably a substance having a gas barrier property against oxygen, water vapor and the like, and preferably has transparency.
- the inorganic layer can be formed of an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof.
- acid aluminum, silicon oxide, and magnesium oxide can be preferably used from the viewpoint of excellent barrier properties against gases such as oxygen and water vapor.
- the preferred thickness of the inorganic layer varies depending on the type of inorganic oxide constituting the inorganic layer, but is usually in the range of 2 nm to 500 nm. Within this range, it is sufficient to select a thickness at which the gas nore properties and mechanical properties of the gas nore laminate are good. When the thickness of the inorganic layer is less than 2 nm, there may be a case where sufficient gas noria properties that do not have reproducibility are exhibited in terms of barrier properties against gases such as oxygen and water vapor. When the thickness of the inorganic layer exceeds 500 nm, the gas noriality tends to decrease when the gas nori laminate is pulled or bent.
- the thickness of the inorganic layer is preferably in the range of 5 to 200 nm, more preferably in the range of 10 to 100 nm.
- the inorganic layer can be formed by depositing an inorganic oxide on a substrate.
- the forming method include vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD).
- the vacuum evaporation method can be preferably used from the viewpoint of productivity.
- a heating method in performing vacuum deposition any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable.
- a plasma assist method or ion Vapor deposition may be performed using a beam assist method.
- a reactive vapor deposition method in which oxygen gas or the like is blown to cause a reaction during vapor deposition may be employed.
- thermoplastic resin film As the substrate on which the gas noble layer of the present invention is formed, a transparent thermoplastic resin film or a thermosetting resin film can be used.
- the thermoplastic resin film is particularly useful as a base material for a gas-nominated laminate used for food packaging materials.
- the base material may have a multilayer structure composed of a plurality of materials.
- thermoplastic resin film for example, polyolefin resin such as polyethylene and polypropylene; polyester resin such as polyethylene terephthalate, polyethylene 2, 6 naphthalate, polybutylene terephthalate and copolymers thereof; Polyamide-based resins such as polyamide 6, polyamide 66, polyamide 12; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyacetate butyl, polycarbonate, polyarylate, recycled cellulose, polyimide, polyetherimide, polysulfone, Examples thereof include films formed by molding polyether sulfone, polyether ether ketone, ionomer resin, and the like.
- polyolefin resin such as polyethylene and polypropylene
- polyester resin such as polyethylene terephthalate, polyethylene 2, 6 naphthalate, polybutylene terephthalate and copolymers thereof
- Polyamide-based resins such as polyamide 6, polyamide 66, polyamide 12
- thermoplastic resin film As the base material of the laminate used for the food packaging material, a film made of polyethylene, polypropylene, polyethylene terephthalate, polyamide 6 or polyamide 66 is preferable.
- the thermoplastic resin film may be an unstretched film or a stretched film, but is preferably a film stretched from the viewpoint of moldability.
- the laminate having the gas noble layer of the present invention may include other layers in addition to the base material and the gas noble layer.
- the mechanical properties can be improved by covering such other layers.
- the gas barrier laminate of the present invention can be easily produced. Since the materials used in the manufacturing method of the present invention and the structure of the laminate are the same as those described above, description of overlapping portions may be omitted.
- a layer made of a composition containing a polymer containing a functional group (carboxylic acid-containing polymer) is formed on a substrate (first step).
- the first step for example, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed And a solution (S) containing at least one metal element-containing compound and a carboxylic acid-containing polymer selected from those in which the compound (L) is completely hydrolyzed and partially condensed And a step of applying the solution (S) to a substrate and drying to form a layer containing the above-described components.
- the solution (S) can be dried by removing the solvent contained in the solution.
- the layer formed on the substrate is brought into contact with a solution containing a metal ion having a valence of 2 or more (second step; hereinafter, this step may be referred to as an ionic step).
- this step at least a part of the functional group (F) (carboxylic acid and Z or carboxylic acid anhydride) contained in the carboxylic acid-containing polymer in the layer is neutralized with a divalent metal ion.
- the ratio of neutralization with divalent metal ions depends on the temperature of the solution containing the metal ions, the concentration of the metal ions, and the immersion time in the solution containing the metal ions. It can be adjusted by changing.
- a solution containing a divalent or higher valent metal ion is sprayed on the formed layer, or a solution containing a divalent or higher valent metal ion on both the base material and the layer on the base material. This can be done by immersing the material in the water.
- the laminate before the ionization step is sometimes referred to as a laminate (A)
- the laminate after the ionization step is sometimes referred to as a laminate (B).
- Solution (S) is compound (L) It can be prepared using a system component, a carboxylic acid-containing polymer, and a solvent. For example, (1) a method in which a compound (L) component is added and mixed in a solvent in which a carboxylic acid-containing polymer is dissolved can be employed.
- compound (A) which is a compound (L) component
- a solvent in which a carboxylic acid-containing polymer is dissolved and then a compound (L) component is added and mixed
- an oligomer one kind of hydrolysis condensate
- a method of mixing the solutions can also be employed.
- the compound (L) component or oligomer thereof may be added alone to the solvent, or may be added to the solvent in the form of a solution in which they are dissolved.
- Preparation method (3) comprises a step of preparing a solution by dissolving a carboxylic acid-containing polymer in a solvent (Stl), and hydrolyzing and condensing compound (L) -based components under specific conditions.
- the solvent used for dissolving the carboxylic acid-containing polymer may be selected according to the type of the carboxylic acid-containing polymer.
- a water-soluble polymer such as polyacrylic acid or polymethacrylic acid
- water is suitable.
- a polymer such as isoprene maleic anhydride copolymer or styrene maleic anhydride copolymer
- water containing an alkaline substance such as ammonia, sodium hydroxide or potassium hydroxide is preferred.
- step (Stl) alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; acetone, methyl ethyl ketone and the like, as long as the dissolution of the carboxylic acid-containing polymer is not hindered.
- Ketones such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; acetone, methyl ethyl ketone and the like, as long as the dissolution of the carboxylic acid-containing polymer is not hindered.
- Ketones such as methanol and ethanol
- ethers such as tetrahydrofuran, dioxane and trioxane
- acetone methyl ethyl ketone and the like
- Ketones such as ethylene glycol and propylene glycol
- Glycol derivatives such as methyl cetosolve, eth
- step (St2) the compound (L) component is hydrolyzed and condensed in a reaction system containing the compound (L) component, an acid catalyst, water, and if necessary, an organic solvent, to form an oligomer. It is preferable to obtain Specifically, a technique used in a known sol-gel method can be applied. When the compound (L) is used as the compound (L) -based component, a gas noor laminate having higher gas barrier properties can be obtained.
- the acid catalyst used in the step (St2) a known acid catalyst can be used.
- oxalic acid or maleic acid can be used.
- hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred.
- Preferred amount of acid catalyst may vary by connexion to the type of catalyst used, the metal atom to 1 mol of the compound (L) -based component, is preferably in the range of 1 X 10- 5 ⁇ 10 mole 1 X 10—more preferably in the range of 4 to 5 moles, even more preferably in the range of 5 X 10 to 1 moles.
- the amount of the acid catalyst used is in this range, the gas nooricity is high and a gas nolia laminate is obtained.
- the preferred amount of water used in the step (St2) varies depending on the type of the compound (L) component, but the alkoxy group or halogen atom of the compound (L) component (when both are mixed) Is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 4 mol, in the range of 0.2 to 3 mol. It is even better to be. Water usage capacity S When the amount is within this range, the resulting gas nore laminate is particularly excellent in gas nore property.
- a component containing water such as hydrochloric acid is used, it is preferable to determine the amount of water used in consideration of the amount of water introduced by the component.
- an organic solvent may be used as necessary.
- the organic solvent to be used is not particularly limited as long as it is a solvent in which the compound (L) component is dissolved.
- alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used as the organic solvent, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group contained in the compound (L) component are more suitable. It is preferably used.
- methanol is preferred for tetramethoxysilane
- ethanol is preferred for tetraethoxysilane.
- the amount of organic solvent used is not particularly limited. However, it is preferable that the concentration of the compound (L) component is 1 to 90% by weight, more preferably 10 to 80% by weight, and even more preferably 10 to 60% by weight.
- the temperature of the reaction system is not necessarily limited when the compound (L) is hydrolyzed and condensed in the reaction system. Usually 2 to: in the range of LOO ° C, preferably in the range of 4 to 60 ° C, more preferably in the range of 6 to 50 ° C.
- the reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0. It ranges from 1 to 6 hours.
- the atmosphere of the reaction system is not necessarily limited, and an atmosphere such as an air atmosphere, a carbon dioxide atmosphere, a nitrogen stream, or an argon atmosphere can be adopted.
- the total amount of the compound (L) component may be added to the reaction system all at once, or may be added to the reaction system in several small portions. . In any case, it is preferable that the total amount of the compound (L) component used satisfies the above-mentioned preferable range.
- the oligomer prepared by the step (St2) preferably has a condensation degree of about 25 to 60% when expressed by the above-mentioned degree of condensation P.
- a solution (S) is prepared by mixing an oligomer derived from the compound (L) component and a solution containing a carboxylic acid-containing polymer.
- the pH of the solution is preferably in the range of 1.0 to 7.0. More preferably, it is in the range of 0. 0. More preferably, it is in the range of 1.5 to 4.0.
- the pH of the solution can be adjusted by known methods, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, It can be adjusted by adding a basic compound such as trimethylamine, pyridine, sodium carbonate or sodium acetate. At this time, if a basic compound that brings about a monovalent cation in the solution is used, a part of the carboxyl group and Z or carboxylic anhydride group of the carboxylic acid-containing polymer can be neutralized with a monovalent ion. The effect that it can be obtained.
- acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia
- a basic compound such as trimethylamine, pyridine
- the solution (S) may be carbonated as long as it does not impair the effects of the present invention.
- Inorganic acid metal salts such as salt, hydrochloride, nitrate, bicarbonate, sulfate, hydrogen sulfate, phosphate, borate, aluminate; oxalate, acetate, tartrate, stearic acid
- Organic acid metal salts such as salts; Acetyl casenatate metal complexes such as aluminum acetyl cetate, metal complexes such as cyclopentagen metal complexes such as titanocene, and cyano metal complexes; layered clay compounds and crosslinking agents
- the above-described polyalcohols and other high molecular compounds, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, and the like may be included.
- the solution) is a metal oxide fine powder produced by wet hydrolysis and polycondensation of the above metal alkoxide; a metal oxide prepared by hydrolyzing, polycondensation or combustion of the metal alkoxide dry Fine powder; water glass power, including fine silica powder, etc.
- the solution (S) prepared in the step (St3) is applied to at least one surface of the substrate.
- the power to treat the surface of the substrate with a known anchor coating agent before applying the solution) You may apply a known adhesive to the surface of the substrate! / ⁇ .
- the method for applying the solution (S) to the substrate is not particularly limited, and a known method can be used. Preferred methods include, for example, a casting method, a date method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kit coating method, a die coating method, a metal ring bar coating method, and a chamber doctor combination. Examples thereof include a coating method and a curtain coating method.
- the solvent contained in the solution (2) is removed to obtain a laminate (laminate (A)) before the ionization step.
- a known method without particular limitation can be applied. Specifically, methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination.
- the drying temperature is not particularly limited as long as it is 15 to 20 ° C or more lower than the flow start temperature of the substrate and 15 to 20 ° C or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer.
- the drying temperature is preferably in the range of 80 ° C to 200 ° C, more preferably in the range of 100 to 180 ° C, and even more preferably in the range of 110 to 180 ° C.
- the removal of the solvent may be performed under normal pressure or reduced pressure.
- the laminate (A) obtained by the above process is brought into contact with a solution containing a metal ion having a valence of 2 or more (hereinafter, sometimes referred to as a solution (Ml)) (ion ion process).
- a solution (Ml)) ion ion process
- a gas barrier laminate is obtained.
- the ionization process may be performed at any stage as long as the effects of the present invention are not impaired.
- the ionization process may be performed before or after being processed into the form of the packaging material, and may be performed after the contents are filled and sealed in the packaging material.
- the solution (Ml) can be prepared by dissolving, in a solvent, a compound that releases a metal ion having a valence of 2 or more upon dissolution (a polyvalent metal compound).
- a solvent used for preparing the solution (Ml) it is desirable to use water, but it may be a mixture of an organic solvent miscible with water and water.
- solvents include lower alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone.
- Ketones Glycols such as ethylene glycol and propylene glycol; Derivatives of glycols such as methyl cetosolve, ethylcetosolve solve, n-butylcetosolve solve; glycerin; acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, dimethoxy An organic solvent such as ethane can be mentioned.
- the polyvalent metal compound compounds capable of releasing metal ions (that is, metal ions having a valence of 2 or more) exemplified with respect to the gas nolia laminate of the present invention can be used.
- metal ions that is, metal ions having a valence of 2 or more
- Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, and zinc acetate.
- the concentration of the polyvalent metal compound in the solution (Ml) is not particularly limited, but is preferably 5
- X 10-4 is in the range of 4 % to 50% by weight, more preferably 1 X 10—in the range of 2 % to 30% by weight, and still more preferably in the range of 1% to 20% by weight.
- the temperature of the solution (Ml) is not particularly limited, but the higher the temperature, the faster the ionization rate of the carboxyl group-containing polymer.
- the preferred temperature is, for example, in the range of 30 to 140 ° C, preferably in the range of 40 ° C to 120 ° C, and more preferably in the range of 50 ° C to 100 ° C.
- a method for removing the solvent a known method without particular limitation can be applied. Specifically, a hot air drying method, a hot roll contact method, an infrared heating method, a microwave heating method and a drying method can be applied alone or in combination of two or more.
- the temperature at which the solvent is removed is particularly limited as long as it is 15 to 20 ° C or more lower than the flow start temperature of the base material and 15 to 20 ° C or more lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. Not.
- the drying temperature is preferably in the range of 40 to 200 ° C, more preferably in the range of 40 to 150 ° C, and even more preferably in the range of 40 to: LOO ° C.
- Solvent removal may be carried out under normal pressure or under reduced pressure! /.
- the layer formed in the first step is heat-treated at a temperature of 120 to 240 ° C after the first step and before and after the second step. It may further include the step of That is, the laminate (A) or (B) may be subjected to heat treatment.
- the heat treatment can be performed at any stage after the removal of the solvent of the coated solution (S) is almost completed!
- the laminate before the ionization step i.e., the laminate (A )
- the temperature of the heat treatment is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 130 to 230 ° C, and still more preferably in the range of 150 ° C to 210 ° C.
- the heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.
- the laminate (A) or (B) may be irradiated with ultraviolet rays!
- the ultraviolet irradiation may be performed any time after the removal of the solvent of the coated solution (S) is almost completed.
- the method is not particularly limited, and a known method can be applied.
- the wavelength of the ultraviolet rays to be irradiated is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm. Also, instead of UV irradiation, you can irradiate with radiation such as electron beams and X-rays.
- Either one of heat treatment and ultraviolet irradiation may be performed, or both may be used in combination.
- heat treatment and irradiation with Z or ultraviolet light By performing heat treatment and irradiation with Z or ultraviolet light, the gas nore performance of the laminate may be enhanced.
- the surface of the base material is treated (treated with an anchor coating agent or applied with an adhesive) before applying the solution.
- the substrate coated with the solution (S) is applied after the first step (application of the solution (S)) and before the heat treatment and the second step (ionization step). It is preferable to carry out an aging treatment that is allowed to stand for a long time at a relatively low temperature.
- the temperature of the aging treatment is preferably 30 to 150 ° C, more preferably 30 to 120 ° C, more preferably 30 to 200 ° C.
- the aging time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and even more preferably in the range of 1 to 5 days.
- the adhesive force between the base material and the gas barrier layer becomes stronger. It is preferable to perform the above heat treatment (heat treatment at 120 ° C to 240 ° C) after this aging treatment! /.
- the gas-noreal laminate of the present invention has excellent transparency, has excellent barrier properties against gases such as oxygen, water vapor, carbon dioxide, nitrogen, etc., and has excellent barrier properties in high humidity. It can be maintained at a high level under both conditions and after being exposed to bending conditions. Even after refining and retort treatment, it exhibits excellent gas noria properties.
- the gas noreal laminate of the present invention has a good gas barrier property that is not influenced by environmental conditions such as humidity, and exhibits a high gas noria property even after being exposed to bending conditions.
- Paper containers are easy to manufacture and can be used for various purposes because they can easily see the contents that do not deteriorate the gas barrier properties during transportation.
- the windowed paper container of the present invention is particularly useful as a food packaging material. Also used as packaging material for packaging chemicals such as agricultural chemicals and medicines Chisaru
- the retort paper container of the present invention has excellent barrier properties against gases such as oxygen, water vapor, carbon dioxide and nitrogen, and the excellent barrier properties are exposed to bending conditions even under high humidity conditions. It is possible to maintain a high level even after it. Excellent gas barrier properties even after retort treatment.
- the paper container of the present invention has a good gas barrier property that is not affected by environmental conditions such as humidity, and exhibits a high gas barrier property even after being exposed to bending conditions, and thus can be applied to various applications.
- the gas noria laminate of the present invention is particularly useful as a food packaging material (particularly a retort food packaging material).
- the gas barrier laminate of the present invention can also be used as a packaging material for packaging chemicals such as agricultural chemicals and pharmaceuticals.
- the vacuum heat insulating material of the present invention can be used for various applications requiring cold insulation and heat insulation. More specifically, refrigerators, freezers, car ceilings, batteries, freezer vessels, refrigerated vessels, heat insulation containers, refrigeration showcases, refrigeration showcases, portable coolers that require heat insulation such as cold insulation and heat insulation, Heating cases for cooking, vending machines, solar water heaters, building materials (walls, ceilings, attics, floors), piping for hot water, cooling water, cryogenic fluid, conduits, clothing, bedding, etc. It can be used as a vacuum insulator.
- the infusion bag of the present invention has transparency and flexibility. Furthermore, it has a high oxygen barrier property before and after heat sterilization treatment, and can prevent alteration of liquid pharmaceuticals such as amino acid infusions, electrolyte infusions, sugar infusions, and infusion fat emulsions due to oxygen.
- the lid material of the present invention has a high oxygen noria property even under high humidity. Also, the oxygen noria property does not deteriorate during processing and transportation. Furthermore, it has environmental suitability.
- the lid material of the present invention can be used as a lid material for containers with lids containing rice, cup ramen, yogurt, fruit jelly, pudding, miso, etc. Can be prevented.
- the laminated tube container of the present invention has a high oxygen noria property and the oxygen barrier property does not decrease even after squeezing. Can be protected. Furthermore, the contents can be seen through, and there is no problem in disposal.
- the laminated tube container of the present invention is used for toiletries such as cosmetics, medicines, pharmaceuticals, and toothpastes. It can be used as a laminated tube container that contains foods such as products, kneads, and wasabi.
- the vacuum packaging bag of the present invention has a reduced gas barrier property due to deformation of the packaging bag such as bending, bending, and expansion during vacuum packaging, and the packaging bag such as expansion and contraction during the heat sterilization treatment that is subsequently applied. Since there is no deterioration in gas barrier properties due to deformation, it is excellent in oxygen barrier properties after vacuum packaging and after vacuum packaging Z Karo thermal sterilization. In addition, the contents can be checked, and it is suitable for the environment.
- the vacuum packaging bag of the present invention has a remarkable effect as compared with the conventional barrier material when the content has a solid content. Examples of such contents include corn with a shaft, rice cake, rice cake, pickles, tea leaves, peanuts, beans, coffee beans, cheese, meat, hamburger, sausage, fish, confectionery, and the like.
- the spouted bouch of the present invention can be manufactured by a conventional bag-making method. It can be formed in any shape and size according to the purpose of use.
- the bag making method for example, a method of forming a single laminate having gasnolia laminate strength used in the present invention or a multilayer laminate including a gas barrier laminate and forming a bag from the laminate is used. Can be adopted.
- bag making such as laminating the body, after laminating the laminated body, heat-sealing the surroundings into a predetermined shape and then making the bag, the plug member obtained by injection molding of polyethylene or polypropylene is attached by heat sealing. That's fine.
- the oxygen permeability was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN10Z50” manufactured by Modern Control Co., Ltd.) with the laminate having a predetermined structure. Specifically, the laminate is set so that the gas noria layer faces the oxygen supply side and the OPET faces the carrier gas side, and the oxygen is used under the conditions of a temperature of 20 ° C, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm. The transmittance (unit: cm 3 Zm 2 'day'atm) was measured. At this time, the humidity was three conditions of 65% RH, 85% RH, and 95% RH, and the oxygen supply side and the carrier gas side were set to the same humidity.
- MOCON OX-TRAN10Z50 manufactured by Modern Control Co., Ltd.
- a brick type paper container having a predetermined structure, and an oxygen permeation measuring device (modern co The oxygen permeability was measured using “MOCON OX-TRAN10Z50” manufactured by Troll. Specifically, the side force of a brick-shaped paper container is also cut out a 6.5 cm diameter circular sample and placed on a 4.5 cm diameter circle opened on a 10 cm square aluminum foil (thickness 30 m). Set the sample and aluminum foil sealed with a two-component curable epoxy adhesive, and transmit oxygen under conditions of a temperature of 20 ° C, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm. The degree (unit: cm 3 Z m 2 'dayatm) was measured. At this time, the humidity was 85% RH, and the oxygen supply side and the carrier gas side had the same humidity.
- the concentration of calcium metal in tap water used for the retort treatment was 15 ppm.
- Example 4 Infusion bags obtained in 1 to 5 were filled with distilled water and subjected to high-pressure steam sterilization under two conditions of 110 ° C, 30 minutes, 135 ° C, 30 minutes or one condition of 110, 30 minutes, respectively. Was applied. The appearance after high-pressure steam sterilization was visually observed. Transparency, shape change (bag breakage, crease), blocking, etc. were observed.
- the oxygen permeability measurement support is taken from the infusion bag whose appearance is observed. The sample was cut off, wiped off the water adhering to the surface with a paper towel, and measured for oxygen permeability. The oxygen transmission rate was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN10Z50” manufactured by Modern Control Company).
- a sample for measuring oxygen permeability was cut from the lid material obtained in the example.
- the oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN10 Z20" manufactured by Modern Control).
- the laminate is set so that the inner layer of the laminate faces the carrier gas side so that the outer layer of the laminate constituting the lid material faces the oxygen supply side, the temperature is 20 ° C, and the oxygen supply Oxygen permeability (unit: cmVm 2 ⁇ day ⁇ atm) was measured under the conditions of 90% RH on the side, 90% RH on the carrier gas, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm.
- the lid material of the present invention a decrease in oxygen barrier property due to physical impact or deformation during processing or transportation is suppressed to a low level. Bending by Gelboflex tester (manufactured by Rigaku Corporation) was used as physical impact and deformation.
- the laminate for the lid material obtained in the example was cut into A4 size, and bent for 200 cycles with a gelbo flex tester. After bending, a sample for measuring oxygen permeability was cut out, and the temperature was 20 ° C, the oxygen supply side humidity was 90% RH, the carrier gas side humidity was 90% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm.
- the oxygen permeability (unit: cmVm 2 ⁇ day ⁇ atm) was measured under the following conditions.
- the laminate tube container force obtained in the example was also cut out from the sample for measuring oxygen permeability.
- the oxygen transmission rate was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN2Z20" manufactured by Modern Control).
- the laminate is selected so that the outer layer of the laminate constituting the lid faces the oxygen supply side and the inner layer of the laminate faces the carrier gas side.
- Oxygen permeability (unit: cmVm 2) under the conditions of temperature 20 ° C, oxygen supply side humidity 90% RH, carrier gas side humidity 90% RH, oxygen pressure 1 atm, carrier gas pressure 1 atm -day a tm).
- the laminate tube container filled with kneaded wasabi was pinched with fingers, and reciprocated along the laminate tube with a finger pressed down with a certain force. After 2000 reciprocations, the kneaded wasabi of the contents was taken out, and a sample for measuring oxygen permeability was cut out from the laminate tube container. The contents were wiped with a paper towel. The measurement of oxygen permeability was carried out under the same conditions as the measurement in (1) above.
- a sample for measuring oxygen permeability was cut from the vacuum packaging bag obtained in the example.
- the oxygen permeability was measured using an oxygen permeation measuring device ("MOCON OX-TR AN2Z20" manufactured by Modern Control).
- the laminate is set so that the inner layer of the laminate faces the carrier gas side so that the outer layer of the laminate constituting the vacuum packaging bag faces the oxygen supply side, and the temperature is 20 ° C and oxygen is supplied.
- the oxygen permeability (unit: cmVm 2 -day atm) was measured under conditions of 85% RH on the side, 100% RH on the carrier gas side, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm.
- Vacuum packaging bag force before and after the retort treatment obtained in the example The sample for measuring oxygen permeability was cut out. The sample was measured for tensile strength at break and tensile elongation at break according to JIS-7127. After conditioning for 7 days in an atmosphere of 23 ° C and 50% RH, a strip-shaped section 15 mm wide and 100 mm long was prepared. Using the film sample, tensile breaking strength and tensile breaking elongation were measured with an autograph AGS-H type manufactured by Shimadzu Corporation under conditions of a chuck interval of 50 mm and a tensile speed of 500 mm Zmin. The measurement was performed for each 10 samples, and the average value was obtained.
- the spouted bout force observed for appearance was cut out from the sample for measuring oxygen permeability, wiped off by lightly pressing the water adhering to the surface with a paper towel, and the oxygen permeability was measured.
- the oxygen transmission rate was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN10Z50” manufactured by Modern Control).
- the laminated body is set so that the outer layer of the laminated body constituting the spouted bouch faces the oxygen supply side so that the inner layer of the laminated body faces the carrier gas side, and the temperature is 20 ° C and oxygen is supplied.
- Oxygen permeability (unit: cmVm 2 ⁇ day ⁇ atm) was measured under conditions of 85% RH on the side, 100% RH on the carrier gas side, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm.
- Example 8 Spout with a spout obtained in 1-2 and Comparative Example 1 was filled with distilled water and dropped 50 times from the side wall of the spout with a spout from a height of 5 m. I celebrated.
- the laminate produced for the above-mentioned evaluation of oxygen barrier properties was used in the ATR (total reflection measurement) mode.
- the c o stretching vibration peak contained in the layer was observed.
- the C O stretching of the carboxyl group after ionization vibration was observed in the range of 1500cm- 1 ⁇ 1600cm _1.
- the maximum absorbance force in each range was calculated, and the ionic strength was determined using the ratio and a calibration curve prepared in advance by the following method.
- a polyacrylic acid with a number average molecular weight of 150,000 is dissolved in distilled water, and a prescribed amount of sodium hydroxide is dissolved.
- the carboxyl group was neutralized with lithium.
- the obtained aqueous solution of neutralized polyacrylic acid was coated on the base material so as to have the same thickness as the gas noble layer of the laminate to be measured for ionicity, and dried.
- PET film (Lumirror (trade name) manufactured by Toray Industries, Inc., thickness 12 / ⁇ ⁇ , hereinafter abbreviated as “ ⁇ ”) was used.
- laminated body layer ZACZOPET made of polyacrylic acid neutralized product
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are made of stretched PET film (OPET; Toray Industries, Ltd. Product name)) on the anchor coat layer by coating and drying A substrate having ACZOPET was prepared.
- the solution (S1) was coated with a bar coater so that the thickness after drying was 1 m, and then dried at 80 ° C. for 5 minutes.
- an anchor coating agent and a solution (S1) were coated on the opposite surface of the stretched PET film. Thereafter, it was further heat-treated in dry air at 200 ° C for 5 minutes.
- Polypropylene (PP) layer Z polypropylene-based adhesive resin (PP-based adhesive) layer Z paper layer ZPP-based adhesive layer Extruded laminate composed of ZPP layer using 400gZm 2 paperboard It was made with. Each PP layer was extrusion-coated at a thickness of 25 ⁇ m, and each PP-based adhesive resin layer was 5 ⁇ m thick, and then a predetermined place was cut out. An adhesive was applied to one surface, and the laminate (B-1) was laminated.
- a non-stretched polypropylene film (CPP) with a thickness of 50 m (Tosero CP RXC-18 manufactured by Toseguchi Co., Ltd.) is applied to the other side of the laminate (B-1) and a PP layer Z paper layer ZPP layer Z laminate (B—D
- a laminate having the structure of ZCPP layer was prepared.
- An anchor coat agent was used as needed when the laminate was prepared.
- a gable-top type paper container with a slot-shaped notch at the position shown was prepared and filled with the contents.
- the sealed liquid paper container produced above has excellent barrier properties against oxygen gas. However, no alteration of the contents was observed, and it was able to withstand distribution in the factory and was excellent in storage and preservation.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- S2 tetramethoxysilane
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S2) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S2). Heat-treated for 5 minutes at 200 ° C.
- AC Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the
- LDPE low density polyethylene
- Extrusion coating was performed and then a predetermined place was cut out.
- Adhesive was applied to one surface, and the laminate (B-2) was laminated.
- the other side of the laminate (B-2) is extrusion-coated with low-density polyethylene (LDPE) to a thickness of 40 ⁇ m, and the LDPE layer Z paperboard ZLDPE layer Z laminate (B-2) is composed of the ZLDPE layer.
- a laminate was produced.
- an anchor coat agent was used as necessary.
- a paper-belt-type paper container having a slot-shaped notch at the position shown in Fig. 1 is produced, and the contents are filled and wrapped.
- the sealed liquid paper container produced above was excellent in barrier properties against oxygen gas, its contents were not altered, and it was able to withstand circulation in a storage area and was excellent in storage and storage.
- Polyacrylic acid ( ⁇ ) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a solution (S3) of an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight was obtained.
- Example 11 Thereafter, the same operation as in Example 11 was carried out except that the solution (S3) was used instead of the solution (S1) to obtain a laminate (1) having a gas barrier layer having a colorless and transparent appearance and good appearance.
- a non-stretched polypropylene film (CPP) (Tosero CP RXC-18 manufactured by Toseguchi Co., Ltd.) with a thickness of 50 m is applied to the other side of the laminate (B-3), and the PP layer Z paper layer ZPP layer Z laminate (B-3)
- a laminate with a ZCPP layer configuration was fabricated.
- an anchor coating agent was used as necessary.
- a paperbell-type paper container having an elongated hole-shaped notch at a position as shown in FIG. 1 was prepared, and the contents were filled and packaged.
- the sealed liquid paper container produced above was excellent in barrier properties against oxygen gas, its contents were not altered, withstood circulation in the factory, and excellent in storage and storage. .
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- a two-component anchor coating agent (AC: Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S1) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S1). Heat-treated for 5 minutes at 200 ° C.
- AC Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the
- a laminate with a gas-clear layer that is colorless and transparent and has a good appearance gas-nore layer (1 ⁇ m) / AC / OPET (12 ⁇ m)) ZACZ gas barrier layer (1 m)
- the body may be the same as the laminate (1).
- polypropylene resin PP was extruded and laminated to a thickness of 20 m each, and adhesive was applied to one side of the laminate.
- B-1 was laminated.
- Adhesive was applied to the other side of the laminate (B-1), and a 50 m thick unstretched polypropylene film (CPP) (Tosero CP RXC-18 from Toseguchi Co., Ltd.) was attached.
- PPZ paperboard ZPPZ laminate B— D ZCPP laminate was prepared. An anchor coat agent was used as needed when producing the laminate. Using this laminate, a brick-type paper container was used.
- the sealed liquid paper container produced above does not change its appearance even after retorting at 120 ° C for 30 minutes. It was excellent in barrier properties, its contents were not altered, and it was able to withstand distribution in the factory and was excellent in storage and storage, etc.
- 20 The oxygen permeability at 85 ° C and 85 ° C was as good as 0.1 cc / m 2 'day atm.
- the oxygen permeability at 20 ° C and 85% RH was 0.30 ccZm 2 'day' atm, which was a very good value. .
- Adhesive is applied to both sides of the 400gZm 2 paperboard, then polypropylene (PP) is extruded and laminated at a thickness of 20 / zm each, adhesive is applied to one side, and biaxially stretched polypropylene film (OPP) was pasted together. Further, an adhesive was applied to the other surface of the OPP, and the laminate (B-1) produced in Example 2-1 was bonded.
- PP polypropylene
- OPP biaxially stretched polypropylene film
- Non-stretched polypropylene film (made by Toseguchi Co., Ltd.) with a thickness of 50 / zm by applying an adhesive to the other side of the laminate (B-1) Tosero CP RXC-18) was laminated to produce a PPZ paperboard ZPPZOPPZ laminate (B— ⁇ ) ⁇ laminate with a CPP configuration.
- an anchor coat agent was used as necessary.
- a brick-type paper container was prepared, and the contents were filled and packaged.
- the sealed liquid paper container manufactured above does not change its appearance even after retort treatment at 120 ° C for 30 minutes, and it has an excellent barrier property against oxygen gas.
- the oxygen permeability at 20 ° C. and 85% RH was as good as 0.10 cc / m 2 'dayatm.
- the oxygen permeability at 20 ° C and 85% RH was 0.30cc / m 2 ⁇ day ⁇ atm. showed that.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- S2 tetramethoxysilane
- two-pack anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S2) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S2). Heat treatment was performed for 5 minutes at 200 ° C.
- this laminate may be a laminate (2) t ⁇ ⁇ ).
- the sealed liquid paper container produced above does not change its appearance even after retort treatment at 120 ° C for 30 minutes, and it has an excellent barrier property against oxygen gas. It was not recognized, and it was able to withstand distribution in the factory and was excellent in storage and preservation.
- the oxygen permeability at 20 ° C and 85% RH was 0.20cc / m 2 'day'atm, which was a very good value.
- oxygen permeability at 20 ° C and 85% RH is extremely good at 40cc / m 2 ⁇ day ⁇ atm. showed that.
- Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S4) having a solid content concentration of 10% by weight in the aqueous solution.
- Example 2-1 the same operation as in Example 2-1 was performed except that the solution (S4) was used instead of the solution (S1), and a laminate (4) having a gas-clear layer having a colorless and transparent appearance was obtained. It was.
- the solution (S4) was used instead of the solution (S1), and a laminate (4) having a gas-clear layer having a colorless and transparent appearance was obtained. It was.
- calcium acetate was dissolved in distilled water to a concentration of 10% by weight, and the aqueous solution was kept at 80 ° C.
- the laminate (4) obtained above was immersed in this aqueous solution (80 ° C .; MI-1) for about 300 seconds. After the immersion, the laminate was taken out, the surface of the laminate was washed with distilled water adjusted to 80 ° C, and then dried at 80 ° C for 5 minutes to obtain the laminate (B-4) of the present invention.
- the neutralization degree of the carboxyl groups of the polyacrylic acid contained in the gas nolia layer was measured by the aforementioned method. As a result, it was found that 95 mol% of the carboxyl groups were neutralized with calcium ions.
- polypropylene resin (PP) was extruded and laminated to a thickness of 20 m each, and adhesive was applied to one side of the laminate.
- B-1 was laminated.
- Adhesive was applied to the other side of the laminate (B-1), and a 50 m thick unstretched polypropylene film (CPP) (Tosero CP RXC-18 from Toseguchi Co., Ltd.) was attached.
- PPZ paperboard ZPPZ laminate (B-4) A laminate with the composition of ZCPP was prepared. In producing the laminate, an anchor coat agent was used as necessary. Using this laminate, a brick-type paper container was prepared and filled with the contents.
- the sealed liquid paper container produced above does not change its appearance even after retorting at 120 ° C for 30 minutes.It also has excellent barrier properties against oxygen gas and changes its contents. It was not recognized, and it was able to withstand distribution in the factory and was excellent in storage and preservation.
- the oxygen permeability at 20 ° C and 85% RH was 1.5cc / m 2 -day 'atm, which was a very good value.
- the oxygen permeability at 20 ° C and 85% RH was 3.2cc / m 2 'dayatm, which was a good value.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- a two-component anchor coat (AC) agent Takelac A 3210 Shobi Takenate 83072, manufactured by Mitsui Takeda Chemical Co., Ltd.
- an aluminum vapor-deposited stretched PET film (VM-PET) (manufactured by Toyobo Co., Ltd.)
- a substrate with an anchor coat layer was prepared by coating on aluminum vapor deposition of E7471) and drying it on the anchor coat layer of this substrate. After coating the solution (S1) with a bar coater to a thickness of 1 m, it was dried for 5 minutes at 80 ° C. Similarly, anchor coating was applied to the opposite side (undeposited side) of the aluminum-deposited stretched PET film.
- laminate (1) gas barrier layer (1 m ) ZAC layer ZVM—PET (12 m) layer ZAC layer / gas noa layer (1 ⁇ m) m)
- Adhesive is applied to one side of the emblem made by the formula company, and OPA layer Z adhesive layer Z laminate (B-1) Z adhesive layer ZLLDPE layer so that the composition of LLDPE film, OPA film and laminate ( B-1) was laminated to obtain a laminate (C-1).
- Lamination was performed so that the aluminum vapor deposition stretched PET film contained in the laminate (B-1) was on the aluminum vapor deposition surface LLDPE layer side.
- FIG. 10 A cross-sectional view of the vacuum insulator is shown in FIG. 10 is vacuum insulation, 11 is packaging material, 12 is continuous It is a core material with urethane foam.
- Two laminates (C-1) were cut into 70 cm ⁇ 30 cm, the LLDPE layers were the inner surfaces, and three sides were heat-sealed to a width of 10 mm to produce a three-sided bag.
- the opening force is also filled with continuous foamed urethane that has been dried for 4 hours in an atmosphere of 120 ° C as a heat insulating core material.
- a vacuum insulator 31 was produced by sealing in an internal pressure of 13 Pa (0. ltorr).
- the vacuum insulator was left at 40 ° C for 90 days, and the internal pressure was measured using a biller vacuum gauge.
- the internal pressure after standing at 40 ° C for 90 days was 20Pa (0.15 torr), a very good value.
- FIG. 13 A cross-sectional view of the vacuum insulator is shown in FIG. 13 is a vacuum insulator, 14 is a packaging material, and 15 is a core material having a continuous foamed urethane force.
- C-2 Two sheets of the above laminate (C-2) cut to 70 cm ⁇ 30 cm were prepared. The CPP layers were the inner surfaces, and three sides were heat-sealed to a width of 10 mm to produce a three-sided bag.
- the opening force is also a heat insulating core material, filled with silica fine powder that has been dried in an atmosphere of 120 ° C for 4 hours in advance, and a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH) at a temperature of 20 ° C and internal pressure
- a vacuum insulator 34 was produced by sealing in a state of 13 Pa (0. ltorr).
- the vacuum insulator was left at 40 ° C for 50 days, and the internal pressure was measured using a biller vacuum gauge.
- the internal pressure after standing at 40 ° C for 90 days was 20 Pa (0.15 torr), which was a very good value.
- Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S3) having a solid content concentration of 10% by weight in the aqueous solution.
- Example 3-1 the procedure of Example 3-1 was performed except that the solution (S3) was used instead of the solution (S1).
- a laminate (1) having a gas barrier layer having a transparent and colorless appearance and a good appearance was obtained.
- Example 3-1 the procedure of Example 3-1 was performed except that the laminate (B-3) was used instead of the laminate (B-1) of Example 3-1, and the vacuum insulator 3 was Produced.
- the vacuum insulation was left at 40 ° C. for 50 days, and then the internal pressure was measured using a biller vacuum gauge.
- the internal pressure after standing at 40 ° C for 90 days was 55Pa (0.42torr), a good value.
- Unstretched linear low-density polyethylene film (LLDPE) with a thickness of 60 m (Sensi L600 manufactured by Daicel Engineering Co., Ltd.) and stretched polyamide film (OPA) with a thickness of 15 m (emblem manufactured by Lucica Corporation) )
- OPA layer Z adhesive layer Z aluminum vapor-deposited stretched PET film Z adhesive layer ZLLDPE layer LLDPE film, OPA film and aluminum vapor-deposited stretched PET film (VM — PET) (Toyobo Co., Ltd. E74 71) was laminated to obtain a laminate (C-3).
- the aluminum vapor deposition stretched PET film was laminated so that the aluminum vapor deposition surface was on the LLDPE layer side.
- FIG. 16 A cross-sectional view of the vacuum insulator is shown in FIG. 16 is a vacuum heat insulator, 17 is a packaging material, and 18 is a core material having a continuous foamed urethane force.
- Two laminates (C-3) were cut into 70 cm x 30 cm, the LLDPE layers were the inner surfaces, and three sides were heat-sealed to a width of 10 mm to produce a three-sided bag.
- the opening force is also filled with continuous foamed urethane that has been dried in an atmosphere of 120 ° C for 4 hours in an atmosphere of 120 ° C, and the temperature is 20 ° C using a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH).
- a vacuum insulator 37 was produced by sealing in an internal pressure of 13 Pa (0. ltorr). The vacuum insulator was left at 40 ° C for 90 days, and the internal pressure was measured using a biller vacuum gauge. Internal pressure after standing at 40 ° C for 90 days is 160Pa (l. 2torr)
- Example 3 Inferior results compared to 1-3.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) and Takenate A50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) is applied to a stretched PET film (OPET; Toray Industries, Ltd.
- a base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S1) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S1). Heat-treated for 5 minutes at 200 ° C.
- Adhesive was applied to one side of 60 / zm unstretched polypropylene film (CPP) (Tosero CP RX C 18 manufactured by Toseguchi Co., Ltd.), CPP layer Z adhesive layer Z laminate (B — 1) Z adhesive layer CPP film and laminate (B-1) were laminated to form the ZCPP layer.
- the laminate CPP layer Z adhesive layer Z laminate (B-1) Z adhesive layer ZCPP layer (laminate (C 1)) 2 sheets were cut into the shape of an infusion bag shown in FIG. . Subsequently, two laminated bodies (C-1) were superposed and the periphery of the cut infusion bag-like sheet was heat sealed, and a polypropylene mouth member was attached by heat sealing to obtain an infusion bag.
- the obtained infusion bag was evaluated for appearance and oxygen barrier property after high-pressure steam sterilization by the above-described method. Under either high pressure at 110 ° C 'for 30 minutes or 135 ° C' for 30 minutes, the appearance did not change compared to before the treatment. That is, the transparency was maintained, and the occurrence of broken bags, wrinkles and blocking was not observed.
- Oxygen permeability under the above-mentioned measurement conditions is as follows: i 10 ° C ⁇ Oxygen permeability after high pressure steam sterilization for 30 minutes is 0.2 cmVm 2 -dayatm, 135 ° C 'High pressure steam sterilization for 30 minutes The oxygen permeability after treatment was 0.1 lcm 3 Zm 2 'dayatm, which was a very good result.
- a laminate for an infusion bag was produced. Apply an adhesive to one side of a 60-m-thick unstretched linear low-density polyethylene film (LLDPE) (Sensi L600 manufactured by Daicel Engineering Co., Ltd.), and then LLDPE layer Z adhesive layer Z laminate (B— 1) Z adhesive layer An LLDPE film and the laminate (B-1) obtained in Example 4-1 were laminated so as to form a ZLLDPE layer.
- the laminate LLDPE layer Z adhesive layer Z laminate (B-1) Z adhesive layer ZCPP layer (laminate (C-2)) 2 sheets are cut into the shape of the infusion bag shown in Fig. 6 by the usual method. did. Subsequently, the two laminates (C 2) are overlaid, the periphery of the cut infusion bag-like sheet is heat sealed, and the mouth member made of linear low density polyethylene is attached by heat sealing to obtain an infusion bag. It was.
- LLDPE linear low-density polyethylene film
- a laminate for an infusion bag was produced.
- Adhesive is applied to one side of the laminate (B-1), high-density polyethylene resin (Novatech HD'LY20 manufactured by Nippon Polychem Co., Ltd.) is extruded onto the adhesive, and a high-density polyethylene (HDPE) layer is laminated by the laminating method.
- HDPE high-density polyethylene
- an adhesive is similarly applied to the opposite side of the laminate (B-1), and high-density polyethylene resin (Novatec HD.LY20 manufactured by Nippon Polychem Co., Ltd.) is extruded to laminate the HDPE layer by the laminating method.
- HDPE layer Z adhesive layer Z laminate (B-1) Z adhesive layer ZHDPE layer (laminate (C-3)) was prepared.
- the two HDPE layers in the laminate (C-3) were extruded and laminated so that the thickness of each layer was 60 ⁇ m.
- Two laminates (C-3) were cut into the shape of the infusion bag shown in FIG. 6 by a usual method. Subsequently, two laminates (C 3) were superposed, the periphery of the cut infusion bag-like sheet was heat sealed, and a high-density polyethylene mouth member was attached by heat sealing to obtain an infusion bag.
- the obtained infusion bag was evaluated for the appearance and oxygen barrier property after high-pressure steam sterilization treatment at 110 ° C for 30 minutes by the method described above. Even under the high-pressure sterilization conditions, there was no change in appearance compared to before the treatment. That is, the transparency was maintained, and the occurrence of bag breaking, wrinkling and blocking was not observed. Regarding the oxygen permeability under the above measurement conditions, the oxygen permeability after high-pressure steam sterilization at 110 ° C. for 30 minutes was 0.4 cmVm 2 -day • atm, which was a very good result.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- S2 tetramethoxysilane
- a two-component anchor coating agent (AC: Takelac A62 6 (trade name) and Takenate A50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) is applied to a stretched PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S2) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S2). Heat-treated for 5 minutes at 200 ° C.
- CPP unstretched polypropylene film
- B— 2 Z adhesive layer CPP film and laminate (B-2) were laminated so as to form a ZCPP layer.
- the obtained infusion bag was evaluated for appearance and oxygen barrier property after high-pressure steam sterilization by the above-described method. 110 ° C for 30 minutes, 135 ° C for 30 minutes Under the above sterilization conditions, the appearance did not change compared to before the treatment. That is, the transparency was maintained, and the occurrence of broken bags, wrinkles and blocking was not observed.
- Oxygen permeability under the above-mentioned measurement conditions is as follows: i Oxygen permeability after high-pressure steam sterilization at 10 ° C for 30 minutes is 0.3 cmVm 2 -dayatm, 135 ° C for 30 minutes under high-pressure steam sterilization The oxygen permeability after treatment was 0.3 cm 3 Zm 2 'day atm, which was a very good result.
- Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S5) having a solid content concentration of 10% by weight in the aqueous solution.
- Example 4-1 Thereafter, the same operation as in Example 4-1 was performed except that the solution (S5) was used instead of the solution (S1), and a laminate (5) having a gas-nolia layer that was colorless and transparent and had a good appearance was obtained. .
- the infusion bag was obtained in the same manner as in Example 4-1, except that the laminate (B-5) was used instead of the laminate (B-1) of Example 41.
- Oxygen permeability under the above measurement conditions is as follows: i Oxygen permeability after high-pressure steam sterilization at 10 ° C for 30 minutes is 2.5 cmVm 2 -dayatm, 135 ° C for 30 minutes under high-pressure steam sterilization The oxygen permeability after the treatment was 3.5 cmVm 2 ⁇ day ⁇ atm, which was a very good result.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, Moly water was added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid to obtain a polyacrylic acid aqueous solution having a solid content concentration of 10 wt% in the aqueous solution.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- two-pack type anchor coating agent (AC; Takelac A62 6 (trade name) and Takenate A50 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) was applied to stretched PET film (OPET; Toray Industries, Ltd.
- a base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S1) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S1). Heat-treated for 5 minutes at 200 ° C.
- Stretched polyamide film manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter sometimes abbreviated as "OPA"
- polypropylene film manufactured by Tosero Corporation, RXC-18 ( Product name), thickness 50 / ⁇ ⁇ , hereinafter abbreviated as “ ⁇ ”
- OPA polypropylene film
- ⁇ thickness 50 / ⁇ ⁇ , hereinafter abbreviated as “ ⁇ ”
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are made of stretched polyamide film (manufactured by Utica Co., Ltd., emblem (trade name)).
- a base material (AC / OPA) having an anchor coat layer was prepared by coating on a thickness of 15 m) and drying to a thickness of 1 m on the anchor coat layer of the base material. After coating the solution (S1) obtained in Example 5-1 with a bar coater, the coating was dried for 5 minutes at 80 ° C. Similarly, the anchor coating agent and the solution ( After that, it was further heat-treated in dry air at 200 ° C.
- This laminated body strength was cut into a predetermined shape to obtain a lid material.
- the oxygen permeability of the lid under high humidity was 0.14 cm 3 Zm 2 'dayatm, a very good value.
- the oxygen permeability after bending was 0.15 cm 3 / m 2 'dayatm, and there was almost no decrease in oxygen permeability compared to before bending.
- Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S3) having a solid content concentration of 10% by weight in the aqueous solution.
- Example 5-1 the same procedure as in Example 5-1 was performed except that the solution (S3) was used instead of the solution (S1) to obtain a laminate (3) having a gas-clear layer having a colorless and transparent appearance. It was.
- Example 5-1 the procedure of Example 5-1 was performed except that the laminate (B-3) was used instead of the laminate (B-1) of Example 5-1, and a lid member was obtained. .
- the oxygen permeability of the lid material under high humidity was 1.5 cm 3 Zm 2 'day.atm.
- the oxygen permeability after bending was 2.8 cm 3 Zm 2 'day atm.
- PAA polyacrylic acid
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S1) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S1). Heat-treated for 5 minutes at 200 ° C.
- AC Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the
- Stretched polyamide film manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter sometimes abbreviated as "OPA"
- polypropylene film manufactured by Tosero Co., Ltd., RXC-18
- ⁇ thickness 50 / ⁇ ⁇ , which may be abbreviated as “ ⁇ ”
- two-part adhesives Mitsubishi Chemical Co., Ltd., ⁇ -385 (product name)
- ⁇ — 5 0 (trade name)
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are made of stretched polyamide film (manufactured by Utica Co., Ltd., emblem (trade name)).
- a base material (AC / OPA) having an anchor coat layer was prepared by coating on a thickness of 15 m) and drying to a thickness of 1 m on the anchor coat layer of the base material. After coating the solution (S1) obtained in Example 6-1 with a bar coater, the coating was dried for 5 minutes at 80 ° C. Similarly, the anchor coating agent and the solution ( After that, it was further heat-treated in dry air at 200 ° C.
- This laminated body strength was cut into a predetermined shape to obtain a lid material.
- the oxygen permeability of the lid under high humidity was 0.14 cm 3 / m 2 'dayatm, which was a very good value.
- the oxygen permeability after bending was 0.15 cm 3 / m 2 'dayatm, indicating that there was almost no decrease in oxygen permeability compared to before bending.
- Polyacrylic acid (PAA) having a number average molecular weight of 150,000 was dissolved in distilled water to obtain a polyacrylic acid aqueous solution (S3) having a solid content concentration of 10% by weight in the aqueous solution.
- Example 6-1 Thereafter, the same operation as in Example 6-1 was performed except that the solution (S3) was used instead of the solution (S1), and a laminate (3) having a gas-clear layer having a colorless, transparent and good appearance was obtained. It was.
- Example 6-1 the procedure of Example 6-1 was performed except that the laminate (B3) was used instead of the laminate (B-1) of Example 6-1 to obtain a lid.
- the oxygen permeability of the lid material under high humidity was 1.5 cm 3 / m 2 'day'atm, which was a good value.
- the oxygen permeability after bending was 2.8 cm 3 Zm 2 'day atm.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- a two-component anchor coating agent (AC: Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S1) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S1). Heat-treated for 5 minutes at 200 ° C.
- AC Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Ltd., Lumirror ( A base material (ACZOPET) having an anchor coat layer was prepared by coating and drying the
- Stretched polyamide film manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter may be abbreviated as “OPA”), and polypropylene film (manufactured by Tosello Co., Ltd., RXC-18) Product name), thickness 50 / ⁇ ⁇ , which may be abbreviated as “ ⁇ ”), and two-part adhesives (Mitsui Takeda Chemical Co., Ltd., ⁇ -385 (product name)) ⁇ — 5 0 (trade name) coated and dried to prepare a gas noa layer ZAC layer ZOPET layer Z AC layer Z gas barrier layer Z printing layer Z adhesive layer ZOPA layer Z adhesive layer ZPP layer Further, an OPA film, a PP film and a laminate (B-1) were laminated to obtain a laminate (B-1-1).
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are made of stretched polyamide film (manufactured by Utica Co., Ltd., emblem (trade name)).
- a base material (AC / OPA) having an anchor coat layer was prepared by coating on a thickness of 15 m) and drying to a thickness of 1 m on the anchor coat layer of the base material.
- the solution (S1) obtained in Example 7-1 was coated with a bar coater, and dried for 5 minutes at 80 ° C.
- the anchor coating agent and the solution After that, it was further heat-treated in dry air at 200 ° C.
- Ji-18 (trade name), thickness 50 111, hereinafter sometimes abbreviated as "PP" A—385 (trade name) and A—50 (trade name)) coated and dried by Chemical Co., Ltd., and prepared a gas barrier layer, ZAC layer, eaves layer, ZAC layer, gas barrier layer, adhesive layer, A laminate ( ⁇ -2-1) was obtained by laminating a ⁇ film and a laminate ( ⁇ -2; gas barrier layer ZAC layer ⁇ layer ZAC layer ⁇ gas noria layer) so as to form a cocoon layer configuration. Two 15 cm ⁇ 30 cm rectangular laminates were cut from this laminate, and the two laminates were overlapped so that the PP layer was inside, and the three sides of the rectangle were heat sealed.
- This heat-sealed bag was filled with a sweet cone with a shaft, the air inside the packaging bag was deaerated, and the last side was heat-sealed. Vacuum packaging was performed with the packaging bag in close contact with the unevenness of the shafted cone. Then 130
- Example 7-2 Except that only the OPA layer was used as the laminate (B-2-1) in Example 7-2, the same operation as in Example 7-2 was performed, and the sample before retorting and the biaxially stretched nylon film were retort.
- PAA polyacrylic acid
- S4 polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- Example 7-1 Thereafter, the same operation as in Example 7-1 was performed except that the solution (S3) was used instead of the solution (S1), and a laminate (3) having a gas-clear layer having a colorless, transparent and good appearance was obtained. It was.
- Example 7-1 the same procedure as in Example 7-1 was performed except that the laminate (B-3) was used instead of the laminate (B-1) of Example 7-1, and the three sides were heat-sealed.
- Manufactured bags This heat-sealed bag was filled with sweet corn with a shaft, the air inside the packaging bag was deaerated, and the last side was heat-sealed.
- Vacuum packaging was performed with the packaging bag in close contact along the unevenness of the sweet corn with a shaft. Thereafter, a retort treatment at 130 ° C. for 30 minutes was performed. Thereafter, a sample for measuring oxygen permeability was cut from the vacuum packaging bag. The oxygen permeability at 85 ° RHZlOO% RH and 20 ° C was 3.3 cmVm 2 ⁇ day ⁇ atm.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- 82.0 parts by weight of methanol 82.0 parts by weight of methanol
- 13.6 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane was dissolved.
- Prepare sol by adding 5.13 parts by weight of distillate and 12.7 parts by weight of 0.1 kg (0.1 N) hydrochloric acid, and hydrolyze and condense for 1 hour at 10 ° C with stirring. Reaction was performed.
- the obtained zeolite was diluted with 185 parts by weight of distilled water, and then quickly added to 634 parts by weight of the 10% by weight polyacrylic acid aqueous solution under stirring to obtain a solution (S1).
- two-component anchor coating agent (AC; Takelac A62 manufactured by Mitsui Takeda Chemical Co., Ltd.) 6 (trade name) and Takenate A50 (trade name) are coated on a stretched PET film (OPET; Lumirror (trade name) manufactured by Toray Industries, Inc.) and dried to form a base material with an anchor coat layer (ACZOPET) Was made.
- the solution (S1) was coated with a bar coater so that the thickness after drying was 1 m, and then dried at 80 ° C. for 5 minutes.
- an anchor coating agent and a solution (S1) were coated on the opposite surface of the stretched PET film.
- this laminate gas nolia layer (1 ⁇ m) ZAC layer ZOPET layer (12 ⁇ m) ZAC layer Z gas barrier layer (1 m)
- this laminate may be referred to as a laminate (1).
- Stretched polyamide film manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter may be abbreviated as "OPA"
- polypropylene film manufactured by Tosero Corporation, RXC-18 ( Product name), thickness 50 / ⁇ ⁇ , which may be abbreviated as “ ⁇ ”)
- two-component adhesives Mitsubishi Chemical Co., Ltd., ⁇ -385 (trade name)
- ⁇ -1; gas nolia layer ACZOPET was coated and dried, and then laminated with the above laminate ( ⁇ -1; gas nolia layer ACZOPET).
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a polyacrylic acid aqueous solution having a solid content concentration of 10% by weight was obtained.
- TMOS tetramethoxysilane
- S2 tetramethoxysilane
- a two-component anchor coating agent (AC; Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Inc., Lumirror ( A base material (ACZOPET) having an anchor coat layer was produced by coating and drying the product on the anchor coat layer of this base material so that the thickness after drying was 1 m. After coating the solution (S2) with a single coater, it was dried for 5 minutes at 80 ° C. Similarly, the other side of the stretched PET film was coated with the anchor coating agent and the solution (S2). Heat-treated for 5 minutes at 200 ° C.
- AC Takelac A62 6 (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.
- Takenate A50 (trade name) are drawn PET film (OPET; manufactured by Toray Industries, Inc., Lumirror ( A base material (ACZOPET) having an anchor coat layer was produced by coating and drying the
- the laminate After the immersion, the laminate is taken out, the surface of the laminate is washed with distilled water adjusted to 80 ° C., and then dried at 80 ° C. for 5 minutes to obtain the laminate (B 2) of the present invention.
- the neutralization degree of the carboxyl groups of the polyacrylic acid in the gas noria layer was measured by the aforementioned method. As a result, it was found that 99 mol% of the carboxyl groups were neutralized with calcium ions.
- Stretched polyamide film manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter sometimes abbreviated as "OPA"
- polypropylene film manufactured by Tosero Corporation, RXC-18 ( Product name), thickness 50 / ⁇ ⁇ , which may be abbreviated as “ ⁇ ”
- two-component adhesives Mitsubishi Chemical Co., Ltd., ⁇ -385 (trade name)
- ⁇ was coated and dried, and laminated with the above laminate ( ⁇ -2; gas barrier layer (AC / OPET)).
- Comparative Example 8 1 Stretched polyamide film (manufactured by UCHIKA CORPORATION, emblem (trade name), thickness 15 m, hereinafter abbreviated as “OPA”), and polypropylene film (manufactured by Tosero Co., Ltd., RXC-18 (trade name) , Thickness 50 / ⁇ ⁇ , which may be abbreviated as “ ⁇ ” below), two-component adhesives (Mitsui Takeda Chemical Co., Ltd., ⁇ -385 (trade name) and ⁇ —5 0 (trade name) was coated and dried, and laminated with aluminum vapor-deposited stretched PET film (VM-PET) (E7471 manufactured by Toyobo Co., Ltd.).
- VM-PET aluminum vapor-deposited stretched PET film
- a laminate (C 3) having a VM-PET Z adhesive ZOPAZ adhesive ZPP and a cage structure was obtained.
- Two laminates VM- ⁇ adhesive ⁇ adhesive ⁇ (laminate C3) were cut into the shape of a spouted bouch shown in FIG. 7 by a usual method.
- the two laminated bodies (C-3) were superposed and the periphery of the cut pouched sheet with a spout was heat sealed, and a polypropylene spout was attached by heat sealing to obtain a spout with a spout.
- oxygen permeability after retort sterilization at 110 ° C 'for 30 minutes is 2.0 cmVm 2 -dayatm, 135 ° C' oxygen permeability after retort sterilization for 30 minutes.
- Polyacrylic acid (PAA) with a number average molecular weight of 150,000 is dissolved in distilled water, and then ammonia water is added to neutralize 1.5 mol% of the carboxyl groups of the polyacrylic acid.
- a solution (S3) of an aqueous polyacrylic acid solution having a solid content concentration of 10% by weight was obtained.
- Example 8-1 Thereafter, the same operation as in Example 8-1 was performed except that the solution (S3) was used instead of the solution (S1), and a laminate (3) having a gas-nolia layer having a colorless and transparent appearance and good appearance was obtained. .
- Example 8-1 the procedure of Example 8-1 was performed except that the laminate (B-3) was used instead of the laminate (B-1) of Example 8-1 to obtain a spout with a spout. It was.
- the spouted bouch thus obtained was subjected to the appearance after retort sterilization treatment, the evaluation of oxygen-noria property, and the drop bag breaking test by the method described above. 110 ° C 'for 30 minutes, 135 ° C for 30 minutes Even under retort sterilization conditions, the appearance change was stronger than before. That is, the transparency was maintained, and the occurrence of broken bags, wrinkles, and blocking was not observed.
- oxygen permeability after retort treatment at 110 ° C 'for 30 minutes is 1.2 cmVm 2 -dayatm, 135 ° C' oxygen permeability after retort treatment for 30 minutes
- the result was very good with 1.6 cm 3 Zm 2 'day atm.
- no broken bag was confirmed (evaluation result ⁇ ).
- the present invention relates to a paper container that has a window that allows the contents to be confirmed, and that is excellent in gas nolianess. It is a paper container that is easy to manufacture, prevents deterioration of its contents for a long period of time, has excellent storability and storage properties, and has little deterioration in storability during transportation.
- the present invention also relates to a retort paper container that can be subjected to a retort sterilization process and is excellent in gas noria. It is a retort paper container that prevents deterioration of the contents over a long period of time and has excellent storage and storage properties.
- FIG. 1 is a perspective view showing an embodiment of a paper container with a window of the present invention.
- FIG. 2 is a cross-sectional view of a main part showing an embodiment of a paper container with a window of the present invention.
- FIG. 3 is a cross-sectional view showing one embodiment of the vacuum heat insulating body of the present invention.
- FIG. 4 is a cross-sectional view of another embodiment of the vacuum heat insulating body of the present invention.
- FIG. 5 is a cross-sectional view of another embodiment of the vacuum insulator.
- FIG. 6 is a front view showing an embodiment of the infusion bag of the present invention.
- FIG. 7 is a view showing an embodiment (standing form) of a spouted bouch according to the present invention.
- FIG. 8 is a view showing an embodiment (a form of a pillow) of a spouted bouch according to the present invention.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Bag Frames (AREA)
- Packages (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES06729950.3T ES2468222T3 (es) | 2005-03-25 | 2006-03-24 | Recipiente de papel |
EP20060729950 EP1870342B1 (en) | 2005-03-25 | 2006-03-24 | Paper container |
US11/909,562 US8158226B2 (en) | 2005-03-25 | 2006-03-24 | Paper container |
CA 2606531 CA2606531C (en) | 2005-03-25 | 2006-03-24 | Paper container |
AU2006229237A AU2006229237B2 (en) | 2005-03-25 | 2006-03-24 | Paper container |
CN2006800182732A CN101184672B (zh) | 2005-03-25 | 2006-03-24 | 纸容器 |
Applications Claiming Priority (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-087370 | 2005-03-25 | ||
JP2005087370 | 2005-03-25 | ||
JP2005-087371 | 2005-03-25 | ||
JP2005087371 | 2005-03-25 | ||
JP2005096784 | 2005-03-30 | ||
JP2005-096786 | 2005-03-30 | ||
JP2005-096784 | 2005-03-30 | ||
JP2005096786 | 2005-03-30 | ||
JP2005101470 | 2005-03-31 | ||
JP2005-101470 | 2005-03-31 | ||
JP2005164319 | 2005-06-03 | ||
JP2005-164318 | 2005-06-03 | ||
JP2005164318 | 2005-06-03 | ||
JP2005164320 | 2005-06-03 | ||
JP2005-164320 | 2005-06-03 | ||
JP2005-164319 | 2005-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006104053A1 true WO2006104053A1 (ja) | 2006-10-05 |
Family
ID=37053311
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/306002 WO2006104053A1 (ja) | 2005-03-25 | 2006-03-24 | 紙容器 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8158226B2 (ja) |
EP (1) | EP1870342B1 (ja) |
KR (1) | KR101211942B1 (ja) |
CN (2) | CN102173321B (ja) |
AU (1) | AU2006229237B2 (ja) |
CA (1) | CA2606531C (ja) |
ES (1) | ES2468222T3 (ja) |
WO (1) | WO2006104053A1 (ja) |
Cited By (2)
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JP2010167765A (ja) * | 2008-12-26 | 2010-08-05 | Kuraray Co Ltd | 紙容器 |
JP2015503468A (ja) * | 2011-12-29 | 2015-02-02 | テトラ・ラヴァル・ホールディングス・アンド・ファイナンス・ソシエテ・アノニムTetra Laval Holdings & Finance S.A. | 包装容器のための包装積層材、ならびに包装積層材から作製される包装容器 |
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JP2010167765A (ja) * | 2008-12-26 | 2010-08-05 | Kuraray Co Ltd | 紙容器 |
JP2015503468A (ja) * | 2011-12-29 | 2015-02-02 | テトラ・ラヴァル・ホールディングス・アンド・ファイナンス・ソシエテ・アノニムTetra Laval Holdings & Finance S.A. | 包装容器のための包装積層材、ならびに包装積層材から作製される包装容器 |
Also Published As
Publication number | Publication date |
---|---|
KR20070119048A (ko) | 2007-12-18 |
CN101184672A (zh) | 2008-05-21 |
EP1870342A1 (en) | 2007-12-26 |
CA2606531C (en) | 2013-11-12 |
CN102173321B (zh) | 2013-07-24 |
CN101184672B (zh) | 2011-04-20 |
AU2006229237B2 (en) | 2011-09-29 |
CN102173321A (zh) | 2011-09-07 |
CA2606531A1 (en) | 2006-10-05 |
US20090297741A1 (en) | 2009-12-03 |
AU2006229237A1 (en) | 2006-10-05 |
EP1870342B1 (en) | 2014-05-07 |
ES2468222T3 (es) | 2014-06-16 |
KR101211942B1 (ko) | 2012-12-13 |
US8158226B2 (en) | 2012-04-17 |
EP1870342A4 (en) | 2013-03-27 |
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